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1.
The isotope dilution (ID) method requires only the measurement of mass and isotopic mass ratios. For this reason, ID is considered a primary method of analysis, capable of higher precision and accuracy than comparative methods used in conventional instrumental analysis, that are based on calibration relative to reference materials. Compared to thermal ionisation mass spectrometers, inductively coupled plasma source-mass spectrometers (ICP-MS) benefit from several practical advantages, including direct liquid sampling at atmospheric pressure, a multi-element capability, high ionisation efficiency, fast scanning capability and widespread availability. These features greatly improve sample throughput, thereby allowing the isotope dilution method to be used on a routine basis. In turn, ID alleviates the need for quantitative sample handling, and thus makes separation of the analytes from matrix elements much easier. This allows ICP-MS instruments to be used under optimal conditions, because it is possible to use advanced, high efficiency sample introduction systems without resorting to large dilution factors. Moreover, the cleanliness of the sampling interface and ion optics is preserved, thereby allowing optimum instrumental performance to be maintained for extended periods, so reducing maintenance costs. Examples are given in this review to highlight the potential of isotope dilution combined with analyte separation for achieving high precision in trace element analysis of geochemical samples.  相似文献   

2.
The influence of non‐spectral matrix effects on the determination of twenty‐two trace elements (Rb, Sr, Y, Cs, Ba, lanthanides, Pb, Th and U) in rock samples using ICP‐MS was investigated. Three types of multi‐element solutions were synthesised containing the twenty‐two trace elements, In, Tl and ten major rock‐forming elements with varying mass fractions mimicking the compositions of basalt, peridotite and dolomite. The synthetic solutions were conditioned to have dilution factors (DF) of 1000–10000. The extent of sensitivity suppression relative to the DF = 10000 solution became more significant for smaller DF solutions, which was not constant across different elements in a single solution but displayed general dependence on m/z. This indicates that at least two internal standards (e.g., In and Tl) are required for the correction of sensitivity variation. On the basis of the results, a new isotope dilution‐internal standardisation method for the determination of twenty‐two trace elements with ICP‐MS was developed, in which the sensitivity variation was corrected by monitoring two enriched isotopes, 113In and 203Tl. This method, coupled with the quantitative correction of interference from oxides and hydroxides, achieved precise determination of twenty‐two trace elements in some rock reference materials with reproducibilities of ±2% for basaltic to andesitic samples.  相似文献   

3.
We present a revised alkali fusion method for the determination of trace elements in geological samples. Our procedure is based on simple acid digestion of powdered low‐dilution (flux : sample ≈ 2 : 1) glass beads where large sample dilution demanded by high total dissolved solids, a main drawback of conventional alkali fusion, could be circumvented. Three geological reference materials (G‐3 granite, GSP‐2 granodiorite and SGD‐1a gabbro) decomposed by this technique and routine tabletop acid digestion were analysed for thirty trace elements using a quadrupole ICP‐MS. Results by conventional acid digestion distinctly showed poor recoveries of Zr, Hf and rare earth elements due to incomplete dissolution of resistant minerals. On the other hand, results obtained by our method were in reasonable agreement with reference data for most analytes, indicating that refractory minerals were efficiently dissolved and volatile loss was insignificant.  相似文献   

4.
建立了激光剥蚀等离子体质谱法直接测定Li2B4O7熔融玻璃中微量元素的分析方法。详细讨论了内标元素的选择及Li2B4O7熔融玻璃的均一性、背景空白对分析测定的影响。以Li2B4O7熔融玻璃中低同位素丰度的6Li作内标，水系沉积物国家标准参考物质熔融玻璃建立多元素标准校正曲线，用于标准参考物质及水系沉积物定值样品的分析，测定值与标准值或溶液雾化等离子体质谱结果比较，具有较好的一致性。  相似文献   

5.
Waters co‐produced during petroleum extraction are the largest waste streams from oil and gas development. Reuse or disposal of these waters is difficult due to their high salinities and the sheer volumes generated. Produced waters (PWs) may also contain valuable mineral commodities. While an understanding of produced water trace element composition is required for evaluating the associated resource and waste potential of these materials, measuring trace elements in brines is challenging due to the dilution requirements of typical methods. Alternatively, inductively coupled plasma‐optical emission spectrometry (ICP‐OES) has shown promise as being capable of direct measurements of trace elements within PWs with minimal dilution. Here, we evaluate direct ICP‐OES trace element quantification in PWs for seventeen trace elements (As, Al, Ba, Be, Cd, Cr, Co, Cu, Hg, Mo, Ni, Pb, Rb, Sb, U, V and Zn) within fifteen PWs from five U.S. continuous reservoirs. The total analytical uncertainties associated with the trace element levels determined using ICP‐OES were estimated to be better than ± 30% (2s) except for Rb, which could not be determined due to ionisation interferences. The ICP‐OES results are compared with trace element levels determined using inductively coupled plasma‐mass spectrometry from the same samples. Our results demonstrate the potential for direct analysis of high‐salinity waters using ICP‐OES with minimal dilution and provide trace element concentrations in waters from several important U.S. petroleum‐generating reservoirs where available data are sparse.  相似文献   

6.
本文以弓长岭铁矿二矿区磁铁石英岩、磁铁富矿和蚀变围岩样品为研究对象,进行了主量元素、微量元素、稀土元素和Fe同位素的测试。结果表明:磁铁石英岩主要由TFe2O3和SiO2组成,Al2O3和TiO2质量分数较低,微量元素质量分数和稀土元素质量分数均较低;经澳大利亚后太古界平均页岩(PAAS)标准化的稀土配分模式呈现出轻稀土亏损和重稀土富集,La、Eu和Y的正异常明显,Ce的异常不明显,Y/Ho值较高;富集Fe的重同位素,且与海底喷发热液经过氧化沉淀后的Fe同位素特征一致。磁铁富矿与磁铁石英岩的地球化学特征有很好的一致性和继承性,但磁铁富矿的REE和Eu质量分数较高,且较磁铁石英岩富集Fe的轻同位素,范围更大,与蚀变岩的Fe同位素组成相近。弓长岭铁矿的磁铁石英岩是陆源物质加入很少的古海洋化学沉积岩,为喷出的海底热液与海水的混合条件下氧化沉淀形成的。磁铁富矿推测为富Fe的轻同位素热液对磁铁石英岩进行改造,经过去硅富铁作用形成的。  相似文献   

7.
12 carbonaceous chondrites, amongst them representatives of nearly all known petrologic types were analyzed for twenty trace elements by spark source mass spectrography combined with the isotope dilution method. Data on different element groups (refractory, moderately volatile and volatile) show that the distribution of the trace elements in the carbonaceous chondrites, with the exception of Renazzo, can be well explained by Anders' two-component model. This is also valid for the highly metamorphosed CV5 chondrite Karoonda.Furthermore, it is observed that the ZrHf-ratios in the carbonaceous chondrites increase with increasing petrologic type which is interpreted as the result of mixing two components with different ZrHf-ratios  相似文献   

8.
陆文  孙骥  周超  郭爱民  彭薇 《地球学报》2020,41(3):384-394
雁林寺金矿位于雪峰弧形构造带(江南造山带湖南段)东段,是湘东北地区一个较为典型的金矿床。本文在前人研究的基础上,统计分析了矿区不同地质体Au元素含量、稀土元素地球化学、微量元素地球化学特征,对比研究了矿区含金石英的H-O同位素、Sr同位素地球化学特征及成矿流体组成特征。提出赋矿围岩冷家溪群浊积岩在沉积阶段就具有明显的金富集。矿区矿石、(矿化)蚀变围岩、未蚀变围岩稀土、微量元素地球化学特征呈现出高度相似性。含金石英的H-O同位素地球化学、Sr同位素地球化学及成矿流体成分特征表明成矿流体为变质流体。综合矿区地质特征、不同地质体金含量、稀土-微量元素地球化学特征、H-O同位素、Sr同位素及成矿流体成分特征,认为地层中的金元素为雁林寺金矿床提供了成矿物质。  相似文献   

9.
稀土稀有稀散元素现代仪器测试全新方法的建立   总被引：1，自引：0，他引：1  
本文系统总结了自2011年以来在三稀矿产实验测试方面取得的新进展。重点介绍了离子相稀土单元素浸泡提取实验研究、稀土原产地Nd同位素与微量元素示踪技术研究、离子吸附型稀土样品野外现场快速定性定量手持X射线荧光(XRF)分析研究成果。结果表明,采用25%硫酸铵浸泡提取,电感耦合等离子体光、质谱(ICP- AES、ICP- MS)测定,可以清晰反映出各稀土元素的浸泡提取率;采用高精度多接收电感耦合等离子体质谱仪(MC- ICP- MS)进行稀土矿石中Nd143/Nd144同位素比值测定,其比值差异可以示踪不同稀土矿石产地;通过精确测试分析不同产地稀土精矿样品中的稀土和其他微量元素含量,并进行数据相关性分析和数据分类分析,通过Y、Be和Bi三种元素含量的比较,可以判断稀土精矿来源;野外现场快速分析,20分钟可完成1件样品测试,不仅可定性判断是否为离子吸附型稀土,同时可定量各离子相稀土单元素含量,与室内精确分析结果符合性良好,可为我国离子吸附型稀土矿床的找矿快速筛查提供技术支撑。 同时介绍了混合酸微波分解样品- 电感耦合等离子体光、质谱(ICP- AES、ICP- MS)同时测定钨矿石、钼矿石、铌钽矿石中的多种稀有稀散稀土元素含量的方案。该方案的特点在于采用了耐氢氟酸体系,尤其对高含量W、Nb、Ta样品更具优势,否则易产生水解,导致测定结果系统偏低。同时梳理总结了我国常见三稀矿石地质样品的特点,针对不同矿种、不同矿床样品类型与基体特点,以及所测试元素种类的不同,研究建立了专门针对“稀有、稀散、稀土元素”现代仪器分析的10个全新的配套方法及其相应的技术指标(准确度、精密度、检出限),可满足地质矿产实验室测试质量管理的规范要求,而且为我国三稀金属矿产资源的战略调查、国家重点研发计划“深地锂资源探测”和四川甲基卡等地找矿突破做出了贡献。  相似文献   

10.
This study reports the results of thirteen rare-earth elements in thirty geochemical reference samples. Three alkali (K, Rb, Cs) and two alkaline earth (Sr, Ba) elements were also determined in eighteen reference samples. The analytical procedure involved is based on spiked samples and later measurement of the rare-earth elements by high-performance liquid chromatography and the alkalies and alkaline earths by thermo-quartz mass spectrometric isotope dilution (THQ-MSID). Whenever possible, the results are compared with literature values.  相似文献   

11.
邵坤  赵朝辉  刘卫 《岩矿测试》2014,33(1):29-33
高纯硝酸银中痕量杂质元素的存在会影响其性能和质量,为提高现代测试技术分析痕量杂质元素的准确度,需要解决的首要问题是通过加入沉淀剂或还原剂将银除去,克服基体元素的基体效应。本文提出采用10 mL 10 g/L柠檬酸-5 g/L乙醇酸作络合保护剂,12 mL 100 g/L氯化铵作沉淀剂,建立了沉淀基体分离-电感耦合等离子体质谱同时测定高纯硝酸银中15种痕量杂质元素的分析方法。探讨了络合剂和沉淀剂浓度及用量、质谱干扰及同位素选择、非质谱干扰及内标选择、实验空白值等因素对测定结果的影响。在最佳的实验条件下,Cu、Pb、Ni、Mn、Au、Pd、Pt、Rh、Ru、Ir元素在0~100 ng/mL,Fe、Hg、Bi、Cr、Sn元素在0~250ng/mL浓度范围内呈良好的线性关系。方法检出限(3σ)为0.005~0.062 ng/g,方法精密度(RSD,n=11)为0.6%~2.6%,加标回收率为94.1%~103.1%。与现行的分析方法相比,本方法采用的络合剂和沉淀剂能将基体元素与杂质元素完全分离而不影响测定结果;实验流程简单快速,检出限低,准确度和精密度均满足了实际样品的分析要求。  相似文献   

12.
Seventeen geochemical reference samples have been analysed for Ag, Te, Pd using mass spectrometric isotope dilution analysis. For most samples, analytical data on these elements were lacking. The concentration range encountered was generally in the nanogram levels.  相似文献   

13.
Chemical speciation of trace metals in aqueous systems is determined by a variety of competitive reactions. Sediments act as sinks for many trace elements, forming surface complexes and otherwise surface-related compounds. Reactions between dissolved trace metals and functional groups at sediment surfaces can be described as coordination reactions similar to those occurring in solution.Factors inherent to both sediment and solution influence the trace metal speciation. These factors include pH, type of mineral, surface area and/or density of reactive surface sites, complexing ligands, and competing ions. The relative importance of some of these factors was studied using an isotope dilution technique. Coastal sediment samples from the Gulf of Mexico were used as the solid matrix. Models developed for pure minerals were used here to (empirically) describe the complex assemblages of minerals in the natural sediment samples.The adsorption experiments showed that cobalt uptake by marine sediment samples followed a two-step time dependency. The initial fast step lasted about five to ten days and the subsequent slow step continued after more than 100 d of equilibration. The pseudoequilibrium reached during the fast step was modeled with an equilibrium model, while the twostep behavior was modeled with a time-dependent model. The two models are related by the reaction stoichiometries. It is believed that the experimental as well as the modeling approach taken in this study, although empirical when used for natural settings, is much more powerful than the use of traditional means to describe trace element interactions with natural solid phases.  相似文献   

14.
We present new reference values for nineteen USGS, GSJ and GIT‐IWG rock reference materials that belong to the most accessed samples of the GeoReM database. The determination of the reference values and their uncertainties at the 95% confidence level follows as closely as possible ISO guidelines and the Certification Protocol of the International Association of Geoanalysts. We used analytical data obtained by the state‐of‐the‐art techniques published mainly in the last 20 years and available in GeoReM. The data are grouped into four categories of different levels of metrological confidence, starting with isotope dilution mass spectrometry as a primary method. Data quality was checked by careful investigation of analytical procedures and by the application of the Horwitz function. As a result, we assign a new and more reliable set of reference values and respective uncertainties for major, minor and a large group of trace elements of the nineteen investigated rock reference materials.  相似文献   

15.
铜同位素地球化学研究及其在矿床学应用的评述和讨论   总被引：3，自引：0，他引：3  
不同地质条件和成矿环境中的铜同位素组成有显著差异,表明利用含铜矿物的铜同位素组成可以作为成矿物质来源的示踪剂.并且,由于铜是主要成矿元素之一,所以铜同位素对于成矿物质来源和成矿过程的示踪更为直接.文章介绍和评述了铜同位素的测试、研究和应用的进展,认为当前对于铜同位素分馏知识的匮乏严重制约着铜同位素研究和应用.从同位素分馏的基本原理出发,提出了铜同位素分馏研究的思路以及可能的分馏规律,对于已发表的部分地质样品测试数据,给出了新的解释,并预测溶解于海水中的铜离子应亏损65Cu.  相似文献   

16.
Concentrations of rare-earth elements (REE), Sc, Fe, Co, Cr, Na and Ir in the bulk sample and mineral separates of the isotopically unique Allende inclusion, EK 1-4-1, were determined by instrumental neutron activation analysis. REE concentrations were also determined by mass-spectrometric isotope dilution for two density separates.The inclusion showed enrichment of light REE over heavy REE with a positive Yb anomaly, thus showing a tendency to resemble group II fine-grained inclusions in REE abundances, although EK 1-4-1 is a coarse-grained inclusion. High Cr concentrations also indicate group II affinity. However, high Ir (6 ppm) and Sc (105 ppm), and low FeO (1.80%), and Co (13.8 ppm) concentrations in the bulk sample and low Na concentrations in mineral separates show group I affinity.Between melilite and pyroxene fractions, the same samples in which mass-fractionated O isotope ratios were observed (Clayton and Mayeda, 1977), REE, Sc, Co and Fe showed distributions which are substantially different from those observed for “ordinary” Allende type B inclusions. These two minerals do not appear to be in equilibrium with respect to trace element distributions.The results indicate that the isotopically unique EK 1-4-1 is also unusual in its elemental abundances and distributions.  相似文献   

17.
The USGS reference glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G were investigated by different analytical techniques. All these materials have a geological (basaltic) matrix and are therefore useful in igneous geochemistry as matrix-matched reference materials for microanalytical techniques. The new GS glasses have trace elements in groups at concentration levels of about < 0.01, 5, 50 and 500 μg g-1. Their major element compositions have been determined by EPMA, and trace elements have been analysed by LA-ICP-MS and two isotope dilution techniques using TIMS and ICP-MS. EPMA and LA-ICP-MS analyses indicated that the USGS reference glasses are homogeneous at the μm to mm scale with respect to major (variations < 1-2%) and most trace elements (variations 1-4%). Trace element data obtained from the different analytical techniques agreed within an uncertainty of 1-5%, indicating that between method results are comparable. Therefore, the preliminary working values for the four USGS GS glasses calculated from these data have a low level of uncertainty.  相似文献   

18.
The United States Geological Survey granitic and granodioritic reference materials G‐2 and GSP‐2 were decomposed in high‐pressure bombs using both HF‐HNO3 and HF‐HNO3‐HClO4 in order to evaluate the feasibility of characterising the entire suite of geologically relevant trace elements through direct analysis with a high‐resolution inductively coupled plasma‐mass spectrometer (HR‐ICP‐MS). The digested samples were diluted to the appropriate levels and analysed at low, medium and high resolution depending on the required sensitivity and potential interferences for each element. Memory effects during analysis of the high field strength elements (HFSE) were negligible when analysed using an all‐Teflon, uncooled sample introduction system and combined with adequate wash times with 4% v/v aqua regia + 0.5% v/v HF between samples. The concentration of the remaining lithophile elements was determined with a conventional, cooled, Scott‐type spray chamber using a wash solution of 1% v/v HNO3. Total procedural blanks contributed between 0.01 to 0.5% to final sample concentrations and blank subtractions were typically unnecessary. Abundances for Li, Hf, Ba, Zr, Ga, Rb, Sr, La, Ce, Th and U were systematically higher, while those for the heavy rare earth elements (HREEs), Cu and Y were systematically lower in this study compared to USGS values for G‐2 and GSP‐2. This is likely to be related to, respectively, higher recoveries from more efficient digestion of refractory phases (i.e., zircon, tourmaline), and better resolution of interferences when using a HR‐ICP‐MS. Sample digestion experiments also showed that perchloric acid digestion in high pressure bombs resulted in superior recoveries and better precision for the bulk of the trace elements analysed. The concentration of the remaining elements overlapped within uncertainty with recommended reference values and with values determined in other studies using isotope‐dilution TIMS, ICP‐MS and XRF. Concentrations for the elements Cd, Sn, Sb, Ta, Bi, Tb, Ni and Mo are also reported for G‐2 and GSP‐2 reference materials. Our study shows therefore that it is feasible to determine thirty‐nine geologically relevant trace elements accurately and directly in granitoid sample digests when using a HR‐ICP‐MS, thereby negating the need for ion exchange or isotopic spiking.  相似文献   

19.
Forty-five selected samples from two different sequences, andfrom different sites spread over the Parana Basin have beenanalysed for major and trace elements and Sr isotope ratios.Results demonstrate the existence of two geochemically and isotopicallydistinct groups, namely a high phosphorus and titanium (HPT)and a low phosphorus and titanium (LPT) group. HPT rocks are relatively rich in LIL elements and have morehomogeneous and markedly lower isotopic Sr ratios than LPT rocks.Since no relationship between the two groups was found, theymay derive from different mantle sources, the HPT source beingmore enriched in most incompatible trace elements except Th,U and Rb than the LPT one. The LPT group, comprising basalts to rhyodacites, displays alarge range in Sr isotopic ratios. This is interpreted as aresult of a fractional crystallization process occurring athigh crustal levels associated with assimilation of crustalmaterial.  相似文献   

20.
Spinel peridotite xenoliths from the Atsagin-Dush volcanic centre, SE Mongolia range from fertile lherzolites to clinopyroxene(cpx)-bearing harzburgites. The cpx-poor peridotites typically contain interstitial fine-grained material and silicate glass and abundant fluid inclusions in minerals, some have large vesicular melt pockets that apparently formed after primary clinopyroxene and spinel. No volatile-bearing minerals (amphibole, phlogopite, apatite, carbonate) have been found in any of the xenoliths. Fifteen peridotite xenoliths have been analysed for major and trace elements; whole-rock Sr isotope compositions and O isotope composition of all minerals were determined for 13 xenoliths. Trace element composition and Sr-Nd isotope compositions were also determined in 11 clinopyroxene and melt pocket separates. Regular variations of major and moderately incompatible trace elements (e.g. heavy-rare-earth elements) in the peridotite series are consistent with its formation as a result of variable degrees of melt extraction from a fertile lherzolite protolith. The Nd isotope compositions of LREE (light-rare-earth elements)-depleted clinopyroxenes indicate an old (≥ 1 billion years) depletion event. Clinopyroxene-rich lherzolites are commonly depleted in LREE and other incompatible trace elements whereas cpx-poor peridotites show metasomatic enrichment that can be related to the abundance of fine-grained interstitial material, glass and fluid inclusions in minerals. The absence of hydrous minerals, ubiquitous CO2-rich microinclusions in the enriched samples and negative anomalies of Nb, Hf, Zr, and Ti in primitive mantle-normalized trace element patterns of whole rocks and clinopyroxenes indicate that carbonate melts may have been responsible for the metasomatic enrichment. Low Cu and S contents and high δ34S values in whole-rock peridotites could be explained by interaction with oxidized fluids that may have been derived from subducted oceanic crust. The Sr-Nd isotope compositions of LREE-depleted clinopyroxenes plot either in the MORB (mid-ocean-ridge basalt) field or to the right of the mantle array, the latter may be due to enrichment in radiogenic Sr. The LREE-enriched clinopyroxenes and melt pockets plot in the ocean island-basalt field and have Sr-Nd isotope signatures consistent with derivation from a mixture of the DMM (depleted MORB mantle) and EM (enriched mantle) II sources. Received: 18 January 1996 / Accepted: 23 August 1996  相似文献   

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