A New Interlaboratory Characterisation of Silicon,Rare Earth Elements and Twenty‐Two Other Trace Element Concentrations in the Natural River Water Certified Reference Material SLRS‐6 (NRC‐CNRC)

The natural river water reference material SLRS‐6 (NRC‐CNRC) is the newest batch of a quality control material routinely used in many international environmental laboratories. This work presents a nine‐laboratory compilation of measurements of major and trace element concentrations and their related uncertainties, unavailable in the NRC‐CNRC certificate (B, Cs, Li, Ga, Ge, Hf, Nb, P, Rb, Rh, Re, S, Sc, Se, Si, Sn, Th, Ti, Tl, W, Y, Y, Zr and REEs). Measurements were mostly made using inductively coupled plasma‐mass spectrometry. The results are compared with equivalent data for the last batch of the material, SLRS‐5, measured simultaneously with SLRS‐6 in this study. In general, very low concentrations, close to the quantification limits, were found in the new batch. The Sr isotopic ratio is also reported.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Rare Earth Element Concentrations in the Natural Water Reference Materials (NRCC) NASS-5, CASS-4 and SLEW-3

The rare earth element and yttrium concentrations of the NRCC reference materials North Atlantic Surface seawater, NASS-5; Coastal Atlantic Surface Seawater, CASS-4; and the estuarine water, SLEW-3 have been precisely determined by ICP-MS after ca. 1:8 preconcentration following a triple chelation using HDEHP (phosphoric acid 2-ethylhexyl ester -mono and di ester mixture) in heptane, and back extraction in nitric acid. We propose reference values with uncertainties for all naturally occurring lanthanides and yttrium.     

Determination of Trace Elements in the Quartz Reference Material UNS-SpS and in Natural Quartz Samples by ICP-MS

A procedure for the digestion and analysis of quartz samples was developed to measure trace element concentrations in natural quartz. The certified glass sand reference material UNS-SpS was chosen to assess the precision, accuracy and detection limit of the analytical method. Quartz was digested with HF/HNO₃ in a closed glassy carbon vessel and analysed by means of quadrupole ICP-MS with external calibration. Analyte concentrations of the sand UNS-SpS were compared with certified and other values from the literature. The abundances of a number of elements (Pr, Gd, Ho and Er) in the reference material are reported here for the first time. The procedure was then applied to three quartz samples from different geological settings to show that trace element data by ICP-MS can distinguish the origin of the sample.     

Determination of Trace Elements in Twenty Six Chinese Geochemistry Reference Materials by Inductively Coupled Plasma-Mass Spectrometry

We report new data for thirty seven elements determined in twenty six Chinese geochemistry reference materials using inductively coupled plasma-mass spectrometry and a reliable and simple dissolution technique. One hundred milligrams of sample were digested with 1 ml of HF and 0.5 ml of HNO₃ in PTFE-lined stainless steel bombs heated to 200 °C for 12 hours. Insoluble residues were dissolved using 6 ml of 40% v/v HNO₃ heated to 140 C for 3 hours. Analytical calibration was accomplished using aqueous standard solutions. Rhodium was used as an internal standard to correct for matrix effects and instrument drift. Precisions were typically better than 5% RSD. Most of the data presented here agree well with the published certified values. For the elements Zr, Hf and most other trace elements, the measured values were less than 10% in error when compared to certified values.     

等离子体质谱法测定天然水中痕量元素

本文利用ICP-MS分析技术检出限低,可同时测定多元素,以及溶液进样等特点,建立了天然水中多种痕量元素分析的有效方法,研究了整个测定质量范围内的背景、干扰及其克服方法,讨论了水中Na、Mg、Ca等元素产生的基体效应对被测元素的影响。对含盐量较低的天然水样,可直接测定的痕量元素达50余种,测定限为0.x—xμg/L。高盐水样如海水、卤水等的测定,本文选择共沉淀法,以Fe(OH)_3为捕集剂,使被测元素与大量的碱金属、碱土金属基体分离。分离后可测40种痕量元素,测定限为0.0x—0.xμg/L。     

Concentrations of Trace Elements in Carbonate Reference Materials Coral JCp-1 and Giant Clam JCt-1 by Inductively Coupled Plasma-Mass Spectrometry

Trace elements in the Geological Survey of Japan carbonate reference materials Coral JCp-1 and Giant Clam JCt-1 were determined by inductively coupled plasma-mass spectrometry after digestion with 2% v/v HNO₃. A standard addition method was adopted in this determination in order to neutralise the Ca matrix effect. In addition, Sc, Y, In and Bi were used as internal standards to control the matrix effect and correct instrumental drift. Of the eighteen elements measured in JCp-1, precisions for fourteen elements, including Cu, Cd and Ba, were better than 10% RSD and concentrations ranged from 0.002 μg g^-1 (Cs) to 8.02 μg g^-1 (Ba). The concentrations of measured trace elements in JCt-1, except for Cu, were lower than those in JCp-1. Precisions for all elements with concentrations higher than 0.04 μg g^-1 in JCt-1 were also better than 10% RSD and concentrations were found to be between 0.001 μg g^-1 (Cs) and 4.84 μg g^-1 (Ba). The concentrations of more than fifteen trace elements in the aragonite reference materials are reported here for the first time. Both reference materials are suitable for use in geochemical studies of environmental reconstruction based upon biogenic carbonate materials.     

A Protocol for the Determination of the Rare Earth Elements at Picomole Level in Rocks by ICP-MS: Results on Geological Reference Materials USGS PCC-1 and DTS-1

Rare earth element analyses are widely used in geology, environmental science and archaeology. Over the past decade inductively coupled plasma-mass spectrometry has become an important source of rare earth data on geological material. However, ICP-MS analysis of rock samples without pre-concentration can be problematic because of complex sample matrices that can generate significant molecular isobaric interferences on rare earth peaks and which need to be corrected. Such problems are exacerbated for ultramafic rocks because the low levels of rare earth elements demand more concentrated solutions in order to maintain signals above background levels. These high solid loads result in intra-run changes in instrument sensitivity which need to be monitored. Pre-concentration chemistries have been developed in order to avoid high solid loads but these are time-consuming and must offer quantitative recoveries or use a yield tracer. Here, we describe an alternative method for rare earth element analysis by ICP-MS, which involves no pre-concentration and is, therefore, able to deliver data rapidly. Our approach is to apply an external correction procedure, based on the analysis of a reference material closely matched in composition to the unknown samples, which allows correction for both interferences and variations in instrument sensitivity. Testing this method, we obtained accurate rare earth element results for basaltic rocks with a precision of about 2% (1s). We demonstrate that the method is also applicable to ultramafic rocks with abundances at ultra-trace (ng g⁻¹) level and present data for twelve separate dissolutions of the peridotite USGS PCC-1 and four separate dissolutions of the dunite DTS-1 reference materials. The repeatability of the data is between 3% and 9% (1s).     

The Preparation and Characteristics of the Geochemical Certified Reference Material BEM (Emeishan Basalt)

A basaltic certified reference material BEM, prepared by Chengdu University of Technology, has recently been approved as a Primary Grade Reference Material (GBW07126) by the General Administration of Quality Supervision, Inspection and Quarantine of China. BEM was sampled from the Emeishan Basalts in China, which is one of the largest basalt provinces in the world. After successfully completing homogeneity and stability tests, collaborative analyses were carried out in seventeen Chinese institutes and laboratories and two American laboratories. More than ten reliable analytical methods based on different principles of measurement were adopted, of which ICP-MS, NAA and ICP-AES contributed 60.5% of all results. Fifty-four elements and oxide components were characterised as certified values, four elements as recommended values and nine elements as information values. A minimum sampling mass of 40 mg for most elements is recommended for use.     

四川稀土矿尾砂的稀土元素和微量元素地球化学特征及开发利用意义

四川是我国轻稀土的重要产地,稀土开采至今已有二十多年的历史,积存了大量尾砂。尾砂中仍然有丰富的稀土资源,但这部分资源究竟有多大的量、能不能再次回收,如何回收,则是当务之急。为查明稀土尾砂中各类元素的分布特征,本文对A、B、C、D四个稀土矿山的尾砂开展了稀土元素和微量元素地球化学特征的初步研究。结果表明:尾砂中稀土元素配分特征继承了原矿石,稀土氧化物含量普遍偏高(0.78%~2.12%),均超过了现行工业指标的边界品位(0.5%~1.0%),且老尾砂的稀土含量高于新尾砂;除了富集稀土元素之外,B尾砂中Sr含量超过10%,C矿区尾砂中Sr含量为2.7%,A矿区尾砂中Ba含量可达1.8%。同时,不同矿区的尾砂中Mo、Bi、Pb、Ag等有用元素发生了不同程度地富集(值得综合回收利用),尤其是Mo达到了边界品位(磁选后的尾砂Mo含量达到2.275%)。本文提出,今后不仅要加强保护四川稀土尾砂,而且需对富集的有用元素采取恰当的方式加以综合回收。     

四川稀土精矿的稀土元素和微量元素地球化学特征及开发利用意义

四川省是我国轻稀土的重要产地,开采近二十年来生产了大量稀土精矿,精矿的稀土品位及其他有用元素组成对矿山资源评价及企业生存至关重要。本文对A、B、C三个稀土矿区稀土精矿的稀土元素和微量元素组成特征进行了研究。结果表明:不同矿区、不同选矿方法、不同企业生产的精矿,其稀土元素和微量元素含量存在显著差异;A矿区浮选精矿的稀土含量最低(ΣREEs=41.57%),而C矿区精矿的稀土含量最高(ΣREEs=55.83%);A矿区磁选精矿的稀土含量(ΣREEs=49.96%)高于浮选精矿(ΣREEs=41.57%);B矿区甲公司(ΣREEs=48.35%)精矿产品的稀土含量高于乙公司精矿产品(ΣREEs=42.92%)。精矿的稀土元素配分特征继承了原矿石的同时普遍亏损Tb和Yb,推测是选矿过程导致了元素的亏损。精矿中除了富集稀土元素,Mo、Bi、Pb、Ga、Th、U、W等有用元素也发生了不同程度的富集,综合利用价值高,尤其是Mo(0.56%)和Ga(0.036%)的含量已达到现行边界品位。本文提出,今后在提高精矿稀土品位的同时,需对富集的元素采取恰当的方式加以综合回收。     

应用电感耦合等离子体质谱法研究西藏甲玛超大型铜多金属矿床辉钼矿稀土元素和微量元素地球化学特征

西藏甲玛超大型铜多金属矿床的钼资源量大于100万吨,辉钼矿是最主要的钼矿物。本文应用电感耦合等离子体质谱法(ICP-MS)分析了不同期次辉钼矿,研究其稀土元素和微量元素的地球化学特征,以指示成矿流体的来源与性质,探讨其成矿机制。结果表明,辉钼矿的稀土元素总量(39.34~168.1μg/g)与斑岩、矽卡岩的稀土元素总量相似,富集轻稀土,且从早到晚总量增加,指示流体源自于岩浆。辉钼矿具有明显的Eu、Ce负异常和Sm正异常,其中Eu负异常指示流体的还原性质;Cu、Pb、Zn等成矿元素含量较高,指示流体中成矿元素的富集。     

新疆小热泉子铜(锌)矿床硫化物显微结构及稀土、微量元素研究

新疆小热泉子铜(锌)矿床位于大南湖晚古生代岛弧带内,矿体主要赋存于一套凝灰质火山碎屑沉积岩中,矿石类型主要为块状黄铜矿矿石、闪锌矿矿石和脉状硫化物矿石.硫化物的显微结构研究表明,黄铁矿主要发生脆型变形,形成碎裂结构、细粒化结构、充填交代结构、“布丁”结构以及变斑晶结构,黄铜矿和闪锌矿发生塑性变形,黄铜矿表现为“S型”面理结构以及在闪锌矿中呈团斑状结构,电子探针结果表明黄铜矿发生明显的活化迁移富集作用.硫化物的稀土微量元素研究表明,闪锌矿中Mn、Ga、As等元素含量很低,Ga/In＜＜1,Ge/In多数小于1,174＜Zn/Cd＜482,In/Cd为0.1 ～ 0.35,不同成矿期黄铁矿的Co/Ni、S/Se、S/Fe比值不同,其稀土元素分配特征与花岗斑岩、流纹斑岩的分配图差别大.通过对硫化物显微结构和稀土、微量元素分布特征的对比研究发现黄铜矿的塑性流动能力比闪锌矿强,在强烈构造作用下使黄铜矿发生活化迁移富集,可能是重要的成矿机制;成矿流体为几种不同性质流体相互作用后的混合物,小热泉子铜锌矿床为早期火山沉积成因,后期为热液叠加改造成因.     

准格尔煤田黑岱沟露天矿煤中稀土及微量元素的分配规律

对准格尔煤田黑岱沟露天矿煤的主量元素、稀土元素和微量元素含量和矿物组成进行了研究。结果表明,黑岱沟露天矿煤中稀土元素平均含量为248.12×10-6,约为中国煤平均值的2.83倍。LREE平均含量为236.66×10-6,HREE平均含量为11.46×10-6,LREE/HREE平均值为20.81,(La/Yb)N平均值为1.59,表明煤中LREE相对HREE富集。煤中部分稀土元素可能富集在勃姆石和黏土矿物中。稀土元素分配曲线δCeS变化区间(0.89～2.21)和δEuS中度亏损(0.46～0.86),验证了沉积环境在煤层形成演化过程中对煤中稀土元素输入的稳定性。黑岱沟煤层中微量元素明显偏高的有Ga、Pb、Se、Sr、Th 和Zr,这些元素的含量高于中国、中国华北晚古生代和美国煤的算术均值,也高于地壳克拉克值。     

电感耦合等离子体发射光谱法测定铀矿石尾渣标准物质中9种痕量元素

样品经ＨＦ－ＨＮＯ３－ＨＣｌＯ４分解,在２ｍｏｌ／ＬＨＮＯ３介质中,采用感耦等离子体光电直读光谱法对铀矿石尾标准物质中的Ａｓ、Ｂａ、Ｂｅ、Ｃｄ、Ｃｒ、Ｎｉ、Ｐｂ等和Ｓｎ进行定值分析。同一样品平行测定６次,其各元素的相对标准偏差在２％－１０％。分析结果均落在标准值的置信区间。     

福建邵武地区张厝萤石矿微量、稀土元素地球化学特征

张厝萤石矿是福建邵武地区典型萤石矿床之一, 萤石矿体赋存于晚侏罗世似斑(少斑)中细粒(细粒)正长花岗岩的断裂构造中, 矿体产状严格受断裂控制。本文对萤石矿石及围岩的微量元素及稀土元素进行了系统分析。微量元素分析结果显示: 亏损高场强元素Nb、Zr及大离子亲石元素Sr、Ba, 富集高场强元素U、Hf、Ti和大离子亲石元素Rb。萤石和围岩稀土配分曲线具有相似同步性, 因此认为研究区萤石的成矿物质来源是相同的, 物源具有相似性。萤石矿稀土元素分布模式为右倾的轻稀土富集型, Eu处出现一个明显“V”形, 表现为负Eu异常、Ce弱正异常, 表明其形成于还原环境中。通过Tb/Ca-Tb/La关系图分析, 说明该萤石矿为热液充填型萤石矿床。综合分析, 认为该萤石矿的成矿物质F和Ca主要来源于热液对围岩的淋滤和萃取, 成矿热液主要来源于大气降水。     

吉林省桦甸油页岩中稀土元素和微量元素的研究

对桦甸油页岩及其灰渣的矿物成分、主量元素、稀土元素和微量元素含量进行测定。结果表明：油页岩中稀土元素含量低于北美页岩(NASC)中的平均含量,REE球粒陨石标准化的分布模式曲线表现为负斜率,(La/Yb)_N的平均值大于1,属于轻稀土富集型;REE北美页岩标准化的分布模式曲线较平缓,（La/Yb）_S的平均值接近于1,轻重稀土分馏不明显。与球粒陨石和北美页岩相比,Eu有较严重的正异常。油页岩中的微量元素与北美页岩和地壳的平均值相比较,Sb、Nb、Cs、Zn、Bi、W等元素具有较高的富集度。油页岩灰渣中稀土元素和微量元素富集度均高于油页岩。     

Precise Determination of Ultra-Low (sub-ng g-1) Level Rare Earth Elements in Ultramafic Rocks by Quadrupole ICP-MS

We present a new method that determines precisely and accurately rare earth elements (REE) at the sub-ng g^-1 level in ultramafic rocks based on acid dissolution and quadrupole ICP-MS with systematic interference corrections on each sample. The method is demonstrated by analyses of the international geochemical reference materials, PCC-1 (peridotite), DTS-1 (dunite) and DTS-2 (dunite) provided by the United States Geological Survey (USGS), and JP-1 (peridotite) issued by the Geological Survey of Japan (GSJ). Detection limits, as rock equivalent, were calculated to be 0.01-0.08 ng g^-1 for our instrument, which is sufficiently low compared to the REE concentrations of ultramafic rocks. In addition, procedural blanks of the proposed method were 0.2-5 pg, which is negligible even for the ultra-low level REE determinations. Reproducibility obtained from separate dissolutions and measurements of USGS DTS-2 and GSJ JP-1 was 3-6%, which corresponds to the high-precision data obtained by ID-TIMS or magnetic sector field ICP-MS with a desolvating nebuliser. The REE data determined exhibit smooth chondrite-normalised REE patterns for all of the tested geochemical reference materials, and the abundances are in good agreement with recently published data.     

Multi‐Element Determination of Trace Elements in Natural Water Reference Materials by ICP‐SFMS after Tm Addition and Iron Co‐precipitation

We report on an improved method for determining trace element abundances in seawater and other natural waters. The analytical procedure involves co‐precipitation on iron hydroxides after addition of a Tm spike, and measurement by inductively coupled plasma‐sector field mass spectrometry (ICP‐SFMS). The validity of the method was assessed through a series of co‐precipitation experiments, using ultra‐diluted solutions of a certified rock reference material (BIR‐1). Results obtained for four natural water reference materials (NASS‐5, CASS‐4, SLEW‐3, SLRS‐4) are in agreement with published working values for rare earth elements, yttrium, vanadium and, when available, for hafnium, zirconium, thorium and scandium. A set of proposed values with uncertainties typically better than 8% RSD is proposed for Hf, Zr and Th.     

西藏努日铜钼钨矿床辉钼矿微量元素、稀土元素地球化学特征——对矿床成矿流体性质的约束

为厘清努日铜钼钨矿床的成矿时代,以矿床中的辉钼矿为研究对象,用ICP-MS分析方法,开展了稀土元素和微量元素地球化学研究。结果显示,辉钼矿具有典型的轻重稀土分馏、轻稀土元素(LREE)富集的右倾配分模式,辉钼矿稀土元素具有强烈的Ce负异常和Eu负异常,前者可能为成矿流体本身具有高温高氧逸度导致,后者可能是与矽卡岩矿化有密切关系的黑云母花岗闪长岩浆在分离结晶过程中大量的斜长石晶出引起的,同时岩体蚀变过程中对成矿流体体系亏损铕有一定贡献。辉钼矿中Pb、Ba、V、Ni、Sr、Rb含量相对较高,U、Th含量非常低,Hf/Sm、Th/La远小于1,Nb/La远大于1,表明成矿流体早期以富F的来自于深部幔源的岩浆热液为主,而Y/Ho、Zr/Hf、Nb/Ta变化范围存在不同幅度的差异。表明主成矿期成矿流体在该阶段不同程度的混入了部分外来流体而富Cl,但总体特征仍以早期成矿流体为主。