Determination of Rare Earth Elements, Sc, Y, Zr, Ba, Hf and Th in Geological Samples by ICP-MS after Tm Addition and Alkaline Fusion

We present a revised method for the determination of concentrations of rare earth (REE) and other trace elements (Y, Sc, Zr, Ba, Hf, Th) in geological samples. Our analytical procedure involves sample digestion using alkaline fusion (NaOH-Na₂O₂) after addition of a Tm spike, co-precipitation on iron hydroxides, and measurement by sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS). The procedure was tested successfully for various rock types (i.e., basalt, ultramafic rock, sediment, soil, granite), including rocks with low trace element abundances (sub ng g⁻¹). Results obtained for a series of nine geological reference materials (BIR-1, BCR-2, UB-N, JP-1, AC-E, MA-N, MAG-1, GSMS-2, GSS-4) are in reasonable agreement with published working values.     

The Direct Determination of Rare Earth Elements in Basaltic and Related Rocks using ICP-MS: Testing the Efficiency of Microwave Oven Sample Decomposition Procedures

Tests are described showing the results obtained for the determination of REE and the trace elements Rb, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th and U with ICP-MS methodology for nine basaltic reference materials, and thirteen basalts and amphibolites from the mafic-ultramafic Niquelândia Complex, central Brazil. Sample decomposition for the reference materials was performed by microwave oven digestion (HF and HNO₃, 100 mg of sample), and that for the Niquelândia samples also by Parr bomb treatment (5 days at 200°C, 40 mg of sample). Results for the reference materials were similar to published values, thus showing that the microwave technique can be used with confidence for basaltic rocks. No fluoride precipitates were observed in the microwave-digested solutions. Total recovery of elements, including Zr and Hf, was obtained for the Niquelândia samples, with the exception of an amphibolite. For this latter sample, the Parr method achieved a total digestion, but not so the microwave decomposition; losses, however, were observed only for Zr and Hf, indicating difficulty in dissolving Zr-bearing minerals by microwave acid attack.     

Temporal and compositional differences between subsolidus and anatectic migmatite leucosomes from the Quetico metasedimentary belt, Canada

Abstract Migmatites in the Quetico Metasedimentary Belt contain two types of leucosome: (1) Layer-parallel leucosomes that grew during deformation and prograde metamorphism. These are enriched in SiO₂, Sr, and Eu, but depleted in TiO₂, Fe₂O₃, MgO, Cs, Rb, REE, Sc, Th, Zr, and Hf relative to the Quetico metasediments. (2) Discordant leucosomes that formed after the regional folding events when metamorphic temperatures were at their peak. These are enriched in Rb, Ba, Sr and Eu, but display a wide range of LREE, Th, Zr, and Hf contents relative to the Quetico metasediments.
Layer-parallel leucosomes formed by a subsolidus process termed tectonic segregation. This stress-induced mass transfer process began when the Quetico sediments were deformed during burial, and continued whilst the rocks were both stressed and heterogeneous. Subsolidus leucosome compositions are consistent with the mobilization of quartz and feldspar from the host rocks by pressure solution. The discordant leucosomes formed by partial melting of the Quetico metasediments, possibly during uplift of the belt. The range of composition displayed by the anatectic leucosomes arises from crystal fractionation during leucosome emplacement. Some anatectic leucosomes preserve primary melt compositions and have smooth REE patterns, but those with negative Eu anomalies represent fractionated melts, and others with positive Eu anomalies represent accumulations of feldspar plus trapped melt.     

Determination of Rare Earth Elements, Y, Th, Zr, Hf, Nb and Ta in Geological Reference Materials G-2, G-3, SCo-1 and WGB-1 by Sodium Peroxide Sintering and Inductively Coupled Plasma-Mass Spectrometry

Data are reported for rare earth elements (REE), Y, Th, Zr, Hf, Nb and Ta in four geological reference materials using sodium peroxide (Na₂O₂) sintering and inductively coupled plasma-mass spectrometry. The described procedure was used by students during their thesis work. A compilation of their reference material data acquired over one year of laboratory work demonstrates the ease and reliability of the method and the high reproducibility of the analytical results. Relative standard deviations of up to thirty six measurements of one reference material were lower than 5% for Y and the REE. Reproduciblities of Zr, Hf, Nb, Ta and Th were higher at between 5% and 10%, and can be attributed to the inhomogeneous distribution of zircon and other trace mineral phases and uncorrected drift effects. The concentration data are compared to reference and literature values and demonstrate that the procedure is also accurate. New data on G-3 show some systematic deviations from G-2, which are statistically significant.     

滇东南晚二叠世铝土矿地球化学特征及物源分析

滇东南地区晚二叠世铝土矿属典型的喀斯特型铝土矿,矿体赋存于上二叠统吴家坪组(龙潭组),分析其地球化学特征对研究其物质来源具有重要意义。全岩分析显示铝土矿石成分以Al₂O₃、Fe₂O₃、SiO₂和TiO₂为主,其中Al₂O₃与Fe₂O₃ 、SiO₂具有较好的负相关关系。微量元素Cr、Zr、 Hf、Ta、Th、U和稀土元素在铝土矿矿化过程中不断富集,元素Zr-Hf、Nb-Ta之间具有明显的正相关关系。lgCr-lgNi图解、稳定元素比值(Zr/Hf)及稀土元素配分模式等地球化学特征说明峨眉山玄武岩为铝土矿的形成提供了主要的物质来源,同时下伏碳酸盐岩也提供了部分成矿物质。     

甘肃西部红柳峡火山颈火山岩地球化学特征及意义

红柳峡火山颈是甘肃西部中生代以来唯一且保存完好的陆相火山口,颈内主要由玄武粗安岩充填,其w(SiO2)=51.79%～52.57%,w(Al2O3)=15.22%～16.38%,w(Na2O+K2O)=6.0%～7.00%,w(Na2O)>w(K2O),w(MgO)=5.02%～6.44%,Mg#=57～65,显示高铝、富镁及富钠贫钾之特征。区内火山岩形成于陆内伸展构造背景,源于过渡型地幔,Zr=254.2×10-6～290.2×10-6、Hf=5.595×10-6～6.313×10-6,Nb=30.85×10-6～34.52×10-6,Zr/Y=9.85～10.15,Hf/Th=0.98～1.04,Hf/Ta=3.05～3.20。Zr/Nb=8.24～8.63,接近于地壳平均值,表明在岩浆作用过程中可能发生过地壳混染作用。火山岩ΣREE含量高(294.49×10-6～334.04×10-6),并表现出轻稀土明显富集且轻稀土元素之间具明显的分馏作用,LREE/HREE=13.78～14.81,(La/Yb)N为18.99～21.56,重稀土元素之间分馏相对较弱,表现为重稀土分布曲线较为平坦,(Gd/Yb)N为2.58～2.73,无明显的Eu异常(δEu=0.93～0.99)和Ce异常(δCe=0.97～1.00),表明在岩浆演化过程中斜长石并未发生分离结晶作用以及上地壳物质的混染作用。可明显区分出早白垩世、晚白垩世及古近纪三期火山岩,表明火山颈形成时间为古近纪。红柳峡火山岩形成时代、构造属性及动力学背景的确定对于研究阿尔金断裂、北祁连北缘断裂有着十分重要的意义。     

浙江治岭头地区霏细岩锆石U-Pb年龄、地球化学特征及形成背景

通过对浙江治岭头地区的霏细岩进行较为系统的LA-ICP-MS锆石U-Pb定年及全岩地球化学分析,探讨了晚白垩世华南地区的构造演化.定年结果显示霏细岩年龄为(98.31±0.92)Ma,为燕山期岩浆侵入活动的产物.岩石为高钾钙碱性偏铝质系列,富SiO2(68.17％～72.90％)、Al2 O3(13.58％～16.07...     

The Zr/Hf ratio as a fractionation indicator of rare-metal granites

The Zr-Hf geochemical indicator, i.e., the Zr/Hf ratio (in wt %) in granitic rocks is proposed to be used as the most reliable indicator of the fractionation and ore potential of rare-metal granites. It was empirically determined that the fractional crystallization of granitic magma according to the scheme granodiorite → biotite granite → leucogranite → Li-F granite is associated with a decrease in the Zr/Hf ratio of the granites. The reason for this is the stronger affinity of Hf than Zr to granitic melt. This was confirmed by experiments on Zr and Hf distribution between granitic melt and crystals of Hf-bearing zircon (T = 800°C, P= 1 kbar). The application of the Zr/Hf indicator was tested at three classic territories of rare-metal granites: eastern Transbaikalia, central Kazakhstan, and the Erzgebirge in the Czech Republic and Germany. The reference Kukul’bei complex of rare-metal granites in eastern Transbaikalia (J₃) is characterized by a uniquely high degree of fractionation of the parental granitic melt, with the granites and their vein derivatives forming three intrusive phases. The biotite granites of phase 1 are barren, the leucogranites of phase 2 are accompanied by greisen Sn-W mineral deposits (Spokoininskoe and others), and the final dome-shaped stocks of amazonite Li-F granites of phase 3 host (in their upper parts) Ta deposits of the “apogranite” type: Orlovka, Etyka, and Achikan. The Kukul’bei Complex includes also dikes of ongonites, elvanes, amazonite granites, and miarolitic pegmatites. All granitic rocks of the complex are roughly coeval and have an age of 142±0.6 Ma. The Zr/Hf ratio of the rocks systematically decreases from intrusive phase 1 (40–25) to phases 2 (20–30) and 3 (10–2). Compared to other granite series, the granites of the Kukul’bei Complex are enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but are depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From earlier to later intrusive phases, the rocks become progressively more strongly enriched or depleted in these elements, and their Zr/Hf ratio systematically decreases from 40 to 2. This ratio serves as a reliable indicator of genetic links, degree of fractionation, and rare-metal potential of granites. Greisen Sn, W, Mo, and Be deposits are expected to accompany granites with Zr/Hf < 25, whereas granites related to Ta deposits should have Zr/Hf < 5.     

Determination of Chlorine in Nine Rock Reference Materials by Isotope Dilution Mass Spectrometry

A procedure for the determination of chlorine by the isotope dilution technique (ID) using negative thermal ionisation mass spectrometry (N-TIMS) is described. Silicate samples of about 10 mg were spiked and decomposed with hydrofluoric acid, and chlorine was isolated by precipitation of silver chloride after neutralisation with Ca(OH)₂. The ammonical solution of AgCl was then subjected to N-TIMS. Replicate analyses of rock reference materials, typically of JB-1 and JR-1, demonstrated the high quality of the analyses (precision for Cl was ± 1-2%). We present here the most precise data sets of chlorine concentrations in nine igneous rock reference materials, three basalts (JB-1, JB-2, JB-3), two andesites (JA-3, AGV-1), two rhyolites (JR-1, JR-2) and two granodiorites (JG-3, GSP-1). The chlorine concentrations found ranged from 152 μg g-1 in AGV-1 to 1008 μg g^-1 in JR-1. Our results presented here are partly (but not completely) in agreement with recommended values, where they are available. The N-TIMS ID technique can thus be used as a means of determining low chlorine contents in silicate materials to high precision.     

冀东-辽西中-晚三叠世柏杖子花岗质侵入岩地球化学、Sr-Nd-Hf同位素特征及岩石成因

关于冀东-辽西中-晚三叠世具有埃达克质岩石特征的花岗质岩石的源区性质,存在较大争议,且以往对位于其北东向隆起区内的柏杖子岩体的成因研究程度低.对柏杖子花岗质侵入岩进行了系统的年代学、地球化学、Sr-Nd-Hf同位素研究,结果显示:柏杖子岩体结晶年龄为233±3 Ma,岩石具有低MgO、Mg#和Co、Ni、Cr含量;富集大离子亲石元素,亏损高场强元素,显示明显的Pb、Th正异常和Nb、Ta、Ti、P负异常;轻、重稀土元素分馏明显;87Sr/86Sr (t) 为0.704 45~0.705 24,ε_Nd(t) 值为-7.3~-1.7;锆石ε_Hf(t) 为-13.4~-5.9.综合分析认为,高Sr/Y比值和低Y含量的柏杖子岩体属于华北克拉通正常厚度镁铁质下地壳熔融的产物,岩石高Sr/Y比值、低Y含量和Nb-Ta负异常特征为继承的华北克拉通下地壳内在性质,并具有与太古宙-古元古代TTG岩石系列相一致的Nb-Ta解耦特征,表明柏杖子岩体源区物质有TTG岩石的贡献;岩石Sr-Nd-Hf同位素组成和低相容元素含量特征同样表明岩浆来源于受改造的下地壳熔融.早中生代玄武岩底侵过程中幔源组分的加入对华北克拉通下地壳形成改造,同时提供热源诱发下地壳物质熔融,形成的熔体向浅表侵位,经历一定程度的斜长石分离结晶,并最终形成柏杖子岩体.      

Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials

Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO₄) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using ²⁹Si and ⁴⁴Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.     

Flux‐Free Fusion of Silicate Rock Preceding Acid Digestion for ICP‐MS Bulk Analysis

We present a new method for the decomposition of silicate rocks by flux‐free fusion in preparation for whole‐rock trace element determination (Sc, Rb, Sr, Y, Zr, Nb, Cs, Ba, rare earth elements and Hf) that is especially applicable to zircon‐bearing felsic rocks. The method was verified by analyses of RMs of mafic (JB‐1a, JB‐2, JGb‐1) and felsic rocks (JG‐3, JR‐3, JSd‐1, GSP‐2, G‐2). Pellets of powdered sample (up to 500 mg) without flux were weighed and placed in a clean platinum crucible. The samples were then fused in a Siliconit® tube furnace and quenched to room temperature. The optimum condition for the fusion of granitic rock was determined to be heating for 2–3 min at 1600 °C. The fused glass in the platinum crucible after heating was decomposed using HF and HClO₄ in a Teflon® beaker. Decomposed and diluted sample solutions were analysed using a quadrupole inductively coupled plasma‐mass spectrometer. Replicate analyses (n = 4 or 5) of the RMs revealed that analytical uncertainties were generally < 3% for all elements except Zr and Hf (～ 6%) in JG‐3. These higher uncertainties may be attributed to sample heterogeneity. Our analytical results for the RMs agreed well with recommended concentrations and recently published concentrations, indicating complete decomposition of our rock samples during fusion.     

下扬子地区下寒武统幕府山组黑色岩系地球化学特征及其地质意义

为探讨下扬子地区下寒武统幕府山组底部富有机质黑色岩系的物源属性及源区构造背景特征,在南京幕府山剖面幕府山组底部系统的采集样品,并对其进行地球化学测试与分析。Th/Sc?Zr/Sc图解表明幕府山组黑色岩系未曾经历沉积再循环;通过分析主量元素比值特征、稀土元素（REE）配分模式、δEu、（La/Yb）_N及La/Th?Hf和La/Yb?∑REE判别图解,认为幕府山组黑色岩系源岩主要是花岗岩和富含长英质矿物的沉积岩等上地壳长英质岩石,存在基性岩的混入。从物源属性、地质年代关系、华南大陆构造演化历程等多方面考虑,源岩中花岗岩成分主要为新元古时期岩浆活动形成的岩浆岩,物源区为江南古陆（江南造山带）。通过分析K₂O+Na₂O?SiO₂、K₂O/Na₂O?SiO₂/Al₂O₃、La?Th?Sc、Th?Co?Zr/10和Th?Sc?Zr/10图解,认为幕府山组黑色岩系源区构造背景为被动大陆边缘。     

江苏赣榆县石桥片麻岩地球化学和锆石U-Pb年龄

通过野外和室内研究结果表明,石桥片麻岩是由沉积岩变质组成。在化学成分上,表现为高硅（SiO₂=75.22%～76.42%）、低铝（Al₂O₃=11.02%～12.29%）、富碱（Na₂O+K₂O=8.00%～8.68%）和贫钙（CaO=0.30%～0.82%）,富集Rb、Ba、Th、U等大离子亲石元素,贫Nb、Ta、Zr、Hf、Ti 等高场强元素,以及轻稀土相对富集（LREE/HREE=6.06～7.14）、铕负异常较明显（δEu=0.18～0.56）等。通过锆石成因类型及定年研究,获得超高压变质作用时间为254 Ma和退变质作用时间为217 Ma,老核（继承锆石）岩浆碎屑锆石是异地多时代（元古代-古生代）,其寄主岩的原岩为沉积岩,时代不会早于古生代。     

东天山阿拉塔格花岗岩体地球化学特征及其构造意义

位于中天山地块南缘大黑山地区的阿拉塔格花岗岩体,岩性主要由花岗闪长岩、二长花岗岩、似斑状花岗岩组成,岩石具有高硅(w（SiO₂）为66.29%~77.47%)、富碱(w（Na₂O+K₂O）为6.75%~9.93%)、高铝(w（Al₂O₃）为10.97%~14.40%)、低Sr(w（Sr）为（28.78~153.00）×10^-6,平均为99.23×10^-6)、低Ti（w（TiO₂）为0.09％~0.77％）的特征。岩石的A/CNK值为1.19~1.50,为钙碱性过铝质岩石;岩石Eu亏损（δEu＝0.19~0.51）、LREE富集(LREE/HREE= 6.80~8.45,(La/Yb)_N= 6.06~9.03),明显富集Rb、Th、K、Hf(Zr) 等大离子亲石元素(LILE),亏损Nb、Ta、P、Ti等高场强元素(HFSE);岩石的Ba含量较低,并具有明显的Sr负异常。结合区域地质特征,通过岩石的地球化学和Sr、Nd同位素综合分析,认为该花岗岩形成于后碰撞环境,且为壳幔混源的岩浆多期次侵位的复合岩体。     

Determination of Rare Earth Elements and Y in Ultramafic Rocks by ICP-MS After Preconcentration Using Fe(OH)3 and Mg(OH)2 Coprecipitation

A simple and reliable method to separate rare earth elements (REE) from Mg, Fe, K, Na, Ca and Ba in ultramafic rocks has been developed, thereby concentrating their abundances. The sample (0.3 g) was digested with HF and HNO₃ in a PTFE bomb, placed in a stainless steel container and, after drying, the insoluble residue was dissolved in 6 ml of 10% v/v HNO₃. Following the addition of 50% triethanolamine and 30% m/v NaOH solution, the REE were precipitated along with Mg(OH)₂, such that the majority of Fe, K and Na in the solution could be separated by centrifuging. The precipitate was dissolved in 1 ml HNO₃ and a buffer solution of NH₄Cl/NH₄OH at pH = 9.0 was added to precipitate the REE along with any remaining Fe as Fe(OH)₃, and so achieve separation from Mg, Ca and Ba, which remained in the solution. In this way, REE could be separated from major elements and were concentrated by a factor of about 60. The recovery of REE was more than 95% using this method. Four ultramafic rock reference materials, PCC-1 (USGS), JP-1 (GSJ), DZE-1, DZE-2 (IGGE) and one new proficiency testing sample GeoPT12 (GAS Serpentinite) were analysed by ICP-MS using indium as an internal standard. The quantitation limits were about 0.02–0.2 ng g⁻¹. Smooth chondrite-normalised REE patterns were obtained with a precision for REE determination of about 2–9%.     

An Evaluation of Methods for the Chemical Decomposition of Geological Materials for Trace Element Determination using ICP-MS

Complete dissolution is essential to obtain accurate analytical results using ICP-MS. In this study, decomposition techniques (i.e. acid digestions using Savillex Teflon vials, a high pressure digestion system and microwave oven, a combined lithium tetraborate fusion - HF/HNO3 acid decomposition and sodium peroxide sinter) for the total dissolution of different types of geological reference materials have been investigated. Savillex Teflon vial HF/HNO3 digestion is effective for basaltic samples. The high pressure HF/HClO4 digestion (PicoTrace TC-805 digestion system, Bovenden, Germany) allows dissolution of basalts and ironstones. Granites and magnetite-rich samples can be dissolved using a high pressure HF/H₂SO₄ method. Geological samples cannot be effectively attacked by microwave acid digestion. A combined lithium tetraborate fusion - HF/HNO3 acid digestion method allows complete dissolution of many different types of geological materials; however, this method precludes the determination of volatile elements due to the high fusion temperature (1000 °C). A sodium peroxide sinter method at 480 °C has the potential for the rapid determination of Y, Sc and REE in different types of geological materials. However, the lack of ultra-pure reagents precludes the use of lithium tetraborate fusion and sodium peroxide sinter methods for the measurement of geological samples with low trace element abundances.     

东天山哈尔里克地区早石炭世A型花岗岩年代学、地球化学及地质意义

A型花岗岩对研究天山造山带壳幔相互作用和构造演化具有重要意义.对东天山哈尔里克地区的碱长花岗岩和正长花岗岩进行了详细的岩石学、地球化学和年代学研究,旨在阐明其成因及构造意义.其中碱长花岗岩的LA-ICP-MS锆石U-Pb年龄为350.7±2.0 Ma和351.8±2.0 Ma,表明该花岗岩体形成于早石炭世早期.岩石含大量碱性长石,暗色矿物以黑云母为主,见钠铁闪石等碱性暗色矿物.岩石高硅、富碱、贫钙镁,富集Rb、Th、K等大离子亲石元素和Zr、Hf等高场强元素,而强烈亏损元素Ba、Sr、Eu,具弱右倾“Ⅴ”字型的稀土分配曲线（（La/Yb）_N=3.23~5.55,δEu=0.19~0.28）.这些矿物学和地球化学特征表明哈尔里克早石炭世花岗岩属高钾准铝质-弱过铝质花岗岩,为典型的A型花岗岩.花岗岩正的ε_Nd（t）值（+4.2~+4.8）和新元古代的二阶段Nd模式年龄（t_DM2=0.71~0.75 Ga）,表明其源区可能为新生年轻地壳,源岩可能是亏损地幔来源的下地壳中基性岩和少量大洋沉积物.结合前人对东天山岩浆活动和构造环境的研究,认为早石炭世哈尔里克与博格达处于同一构造背景下,早石炭世早期A型花岗岩可能形成于博格达弧后裂谷的伸展早期阶段.      

Karst in granitic rocks, South Cameroon: cave genesis and silica and taranakite speleothems

ABSTRACT A cave in granitic rocks was studied in Mezesse, South Cameroon. Coralloid speleothems, draperies and dissolution traces on the cave walls attest to its truly karstic nature. The speleothems consist of microlayers of opal and taranakite (K,NH₄)Al₃(PO₄)₃(OH).9H₂O. They indicate a significant mobilization of silica, Al and K from granite during the formation of the cave. Identification of silicified bacteria in the speleothems layers suggests a possible role of these micro-organisms in silica deposition. The presence of taranakite and of silicified organic remains within the speleothems lead to a better understanding of the genesis of the cave.     

Low-Level Analysis of Lanthanides in Eleven Silicate Rock Reference Materials by ICP-MS After Group Separation Using Cation-Exchange Chromotography

A simple method is described for the determination of lanthanides in depleted rocks based on acid dissolution, cation-exchange chromatography and ICP-MS analysis using a low flow, microconcentric nebuliser. The potential of the method is evaluated by analysis in triplicate of eleven low-concentration level geochemical reference materials (UB-N, NIM-D, BIR-1, DNC-1, JB-2, JGb-1, JGb-2, NIM-N, NIM-P, FK-N and MA-N). The repeatability of the three dissolutions is between 0.2% and 0.6% relative standard deviation (RSD) for basaltic samples BIR-1 and JB-2, with the exception of La in BIR-1 (2.6% RSD), presumably because of blank or memory effects. The results are more scattered for coarsegrained rocks. A good agreement between the results and working values is observed for most mafic samples and the serpentinite UB-N. Significant deviations observed between the data obtained in this work and working values for some reference materials might reflect heterogeneities of the REE distributions in coarse-grained (especially granitic) rocks at the 10 0 mg sub-sampling scale.