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1.
Inductively coupled plasma-mass spectrometry is well suited for the precise, accurate and rapid determination of rare earth elements in most geological samples. However, determination of rare earth elements in certain mantle-derived materials, without applying preconcentration techniques, remains problematical due to low natural concentrations (generally < 1 ng g−1). Consequently, USGS reference materials DTS-1 (a dunite) and PCC-1 (a partially serpentinized harzburgite) have only suggested rather than recommended values for the rare earth elements in reference material compilations. We compared results obtained using two ICP-MS instruments: a U-5000AT ultrasonic nebuliser coupled to a PQ2+ quadrupole ICP-MS and an ELEMENT sector field ICP-MS equipped with a MCN-6000 microconcentric desolvating nebuliser, with the suggested literature values for these two reference materials. Precision and accuracy of analytical methods employed by both instruments were demonstrated by excellent relative standard deviations (< 2%) and inter-laboratory agreement (< 5%) for numerous analyses of BHVO-1 and BIR-1, which are well established with rare earth elements contents at the μg g−1 level. Repeat analyses of DTS-1 and PCC-1 at each laboratory indicate that each method is generally precise to better than 5% at sub-g g−1 levels. Furthermore, values from both instruments generally agree to within 10%. Our DTS-1 and PCC-1 values agree reasonably well with selected data reported in the literature (except for Ce and Sm in DTS-1) but exhibit poorer agreement with reported compilation values. With the demonstrated level of precision and accuracy, we contend that these new values for DTS-1 and PCC-1, generated by two different instruments, are the best estimates of the true whole-rock composition of these samples reported to date.  相似文献   

2.
We found that the suppression of signals for 88Sr, 140Ce and 238U in rock solution caused by rock matrix in ICP-MS (matrix effects) was reduced at high power operation (1.7 kW) of the ICP. To make the signal suppression by the matrix negligible, minimum dilution factors (DF) of the rock solution for Sr, Ce and U were 600, 400 and 113 at 1.1, 1.4 and 1.7 kW, respectively. Based on these findings, a rapid and precise determination method for Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U using FI (flow injection)-ICP-MS was developed. The amount of the sample solution required for FI-ICP-MS was 0.2 ml, so that 1.8 mg sample was sufficient for analysis with a detection limit of several ng g-1. Using this method, we determined the trace element concentrations in the USGS rock reference materials, DTS-1, PCC-1, BCR-1 and AGV-1, and the GSJ rock reference materials, JP-1, JB-1, -2, -3, JA-1, -2 and -3. The reproducibilities (RSD %) in replicate analyses (n=5) of BCR-1, AGV-1, JB-1, -2, -3, JA-1, -2, and -3 were < 6 %, and typically 2.5%. The difference between the average concentrations of this study for BCR-1 and those of the reference values were < 2%. Therefore, it was concluded that the method can give reliable data for trace elements in silicate rocks.  相似文献   

3.
We have developed a rapid and accurate method for the determination of Mo, Sb and W in geological samples using isotope dilution inductively coupled plasma-mass spectrometry with a flow injection system (ID-FI-ICP-MS). The chemical procedure requires HF digestion of the sample with a Mo-Sb-W mixed spike, subsequent evaporation and dissolution of Mo, Sb and W from Mg and Ca fluorides with HF. Recovery yields of Mo, Sb and W in the extraction were > 94% for samples of peridotite, basalt and andesite composition, with the exception of W in samples of peridotite composition for which recovery was 81%. No matrix effects were observed in the determination of the isotope ratios of Mo, Sb and W in solutions prepared from peridotite, basalt and andesite samples down to a dilution factor of 100. Detection limits of Mo, Sb and W in silicate materials were at the several ng g−1 level. Analysis of the silicate reference materials PCC-1, DTS-1, BCR-1, BHVO-1, AGV-1 from the US Geological Survey and JP-1, JB-1, -2, -3, JA-1, -2, and -3 from the Geological Survey of Japan as well as the Smithsonian reference Allende powder yielded reliable Mo, Sb and W concentrations. The repeatability in the analysis of basalts and andesites was < 9%. This technique requires only 0.2 ml sample solution, and is therefore suitable for analyzing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates.  相似文献   

4.
The high sensitivity, minimal oxide formation and single internal standard capability of high resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS) is demonstrated in the direct determination of Sc, Y and REE in the international reference materials: basalts (BCR-1, BHVO-1, BIR-1, DNC-1), andesite (AGV-1) andultramafics (UB-N, PCC-1 and DTS-1). Time consuming ion exchange separation or preconcentration were found to be unnecessary. Smooth chondrite normalized plots of the REE in PCC-1 and DTS-1 were obtained in the range 0.8-50 ng g-1 (0.01-0.1x chondrite). Method precision was found to be digestion dependent with an average external repeatability of 2-4% for the basalts, AGV-1 and UB-N, and 10% for PCC-1 and DTS-1. The mass peak due to 45Sc was completely resolved from 29Si16O and 28Si16O1H spectral interferences using medium resolution, which casts doubt on the accuracy of Sc determinations using quadrupole ICP-MS. Literature values for Y in rock reference materials were found to be approximately 9% high after HR-ICP-MS and XRF analysis.  相似文献   

5.
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.  相似文献   

6.
New concentrations for Au, Ir and Ag obtained by instrumental neutron activation analysis are presented for seventy geochemical reference materials. Results in agreement with literature values for Au and Ir down to concentrations of a few ng g−1 were obtained. For Au and Ir concentrations above 10 ng g−1, the repeatability of replicate analyses of reference materials was mostly better than 10%. For concentrations between 1 and 10 ng g−1 the RSD for Ir was 10–30%, whereas for Au it was higher and more variable (20–50%). In addition, concentrations for Cd and Hg are presented for some of the same reference materials. The high RSD at relatively high concentrations seen in gold for some RMs (e.g., WMG-1, WMS-1) did not exist for Ir and suggests homogeneity for this platinum-group element at the sub-sample size used in this study. For the following eight RMs, mostly ultramafic rocks (CHR-Pt+, OREAS-13P, OREAS-14P, PCC-1, UMT-1, WMG-1, WMS-1, WPR-1), Ir measurements agreed within ± 10% of mostly certified or recommended concentrations, which ranged from 2 ng g−1 to 6 μg g−1. For the reference material UB-N, iridium concentration compared favourably to published results obtained by isotope dilution ICP-MS methods and a previously unrecognised heterogeneity is inferred for Au, Hg and Sb, but not for the other measured elements.  相似文献   

7.
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.  相似文献   

8.
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%.  相似文献   

9.
To evaluate trace element soil contamination, geochemical baseline contents and reference values need to be established. Pedo-geochemical baseline levels of trace elements in 72 soil samples of 24 soil profiles from the Mediterranean, Castilla La Mancha, are assessed and soil quality reference values are calculated. Reference value contents (in mg kg?1) were: Sc 50.8; V 123.2; Cr 113.4; Co 20.8; Ni 42.6; Cu 27.0; Zn 86.5; Ga 26.7; Ge 1.3; As 16.7; Se 1.4; Br 20.1; Rb 234.7; Sr 1868.4; Y 38.3; Zr 413.1; Nb 18.7; Mo 2.0; Ag 7.8; Cd 4.4; Sn 8.7; Sb 5.7; I 25.4; Cs 14.2; Ba 1049.3; La 348.4; Ce 97.9; Nd 40.1; Sm 10.7; Yb 4.2; Hf 10.0; Ta 4.0; W 5.5; Tl 2.3; Pb 44.2; Bi 2.2; Th 21.6; U 10.3. The contents obtained for some elements are below or close to the detection limit: Co, Ge, Se, Mo, Ag, Cd, Sb, Yb, Hf, Ta, W, Tl and Bi. The element content ranges (the maximum value minus the minimum value) are: Sc 55.0, V 196.0, Cr 346.0, Co 64.4, Ni 188.7, Cu 49.5, Zn 102.3, Ga 28.7, Ge 1.5, As 26.4, Se 0.9, Br 33.0 Rb 432.7, Sr 3372.6, Y 39.8, Zr 523.2, Nb 59.7, Mo 3.9, Ag 10.1, Cd 1.8, Sn 75.2, Sb 9.9, I 68.0, Cs 17.6, Ba 1394.9, La 51.3, Ce 93.5, Nd 52.5, Sm 11.2, Yb 4.2, Hf 11.3, Ta 6.3, W 5.2, Tl 2.1, Pb 96.4, Bi 3.0, Th 24.4, U 16.4 (in mg kg?1). The spatial distribution of the elements was affected mainly by the nature of the bedrock and by pedological processes. The upper limit of expected background variation for each trace element in the soil is documented, as is its range as a criterion for evaluating which sites may require decontamination.  相似文献   

10.
Inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the determination of Rb, Sr, Ba, Zr, Hf, Nb, Ta, Th, U, Pb, Sc and 14 REE in peridotites and their constituent minerals: garnet, clinopyroxene, orthopyroxene and olivine. Determination limits for most elements are 1–10 ppb (in the solid sample), with accuracy and precision comparable to those of thermal ionisation and spark-source mass spectrometry. New data on international standards PCC-1, DTS-1, UB-N and JP-1 are reported.  相似文献   

11.
Mineral and whole rocks analyses of 12 Jurassic basalt dykes from Vestfjella, Dronning Maud Land, Antarctica, are presented, and their genesis discussed. On the basis of major oxides and norms the basalts may be classified as olivine and quartz tholeiites. Plotted in the Plag---Cpx---(Opx + 4Q) and Ol---Plag---Q projections, the compositions are most compatible with fractional crystallization of olivine, clinopyroxene and plagioclase from a basalt liquid at very low pressure. The ratios between strongly incompatible elements such as Rb, Cs, Zr, Hf, Ta and Th vary considerably, and petrographic mixing calculations give poor fits with respect to Rb, Cs, Ta, Th and light REE. Initial 87Sr/86 Sr ratios range between 0.70347 and 0.70687, and show no correlation with Rb/Sr or any other SIE ratios. The trace element and Sr isotope data thus do not suggest any simple cogenetic petrogenetic model. It is concluded that the basalt melts most plausibly have been contaminated by, or mixed with anatectic melts of crustal material, rather than reflecting mantle heterogeneity.  相似文献   

12.
The direct analysis of nickel sulfide fire assay buttons by UV laser ablation ICP-MS was used to determine the platinum-group elements and gold in the following reference materials: UMT-1, WPR-1, WMG-1, GPt-4, GPt-6 and CHR-Bkg. The instrument was calibrated with buttons prepared using quartz doped with the appropriate standard solutions. Analytical precision (RSD) was generally better than 10%, although occasional higher RSDs may infer local heterogeneities within nickel sulfide buttons. Good or excellent agreement was observed between analysed and reference material values except Rh in UMT-1 and WMG-1, which suffered an interference from copper. Detection limits calculated as 10 s quantitation limits were Au (1.7 ng g−1), Pd (3.3 ng g−1), Pt (8.3 ng g−1), Os (1.3 ng g−1), Rh (1 ng g−1), Ru (5 ng g−1) and Ir (0.7 ng g−1).  相似文献   

13.
利用中国癌死亡率与土壤坏境中化学元素的相关性成果,研究了四川省癌死亡率与土壤环境中化学元素:As、Cd、Co、Cu、Hg、Mn、Ni、Pb、Se、V、Li、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、B、Al、Ga、In、Tl、Sc、Y、La、Ce、Pr、Nd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Th、U、Sn、Ti、Zr、Hf、Sb、Bi、Ta、Te、Mo、W、Br、I、Fe等52个元素含量的关系  相似文献   

14.
The analysis of granitic pegmatites still remains a challenge because suitable natural reference materials are scarce or not available. Two new reference materials were prepared at the Smithsonian Institution, to provide an avenue to pursue the geochemical analysis of micas and feldspars in granitic pegmatites: STL-1, the Stewart lepidolite (NMNH 174041) and ZA-1, the Zapot amazonite (NMNH 174042). STL-1 was prepared from lepidolite collected from the lithium-rich Stewart pegmatite, San Diego County, California (33°22'52'N, 117°03'41'W). ZA-1 was prepared from an amazonite from the topaz-bearing Zapot pegmatite, Mineral County, Nevada, (38° 41'N, 118 °33'W). The results of this study indicated that STL-1 and ZA-1 are homogeneous and could be used as reference materials that would allow the expansion of calibration curves in XRF analysis up to 16000 μg g−1 for Rb, 2000 μg g−1 for Cs and 100 μg g−1 for Tl. STL-1 and ZA-1 also contain unusually high concentrations of Ga and Tl, and STL-1 of Nb.  相似文献   

15.
本文对塔西北震旦系中的苏盖特布拉克组玄武质岩墙以及塔西南奥陶系玛列兹肯群中辉绿岩脉的区域地质、岩石学、地球化学等进行了对比研究,同时对锆石的微区 U-Pb 同位素年代学及其构造环境等进行了研究。 前者为顺层侵入、包裹了中酸性的捕虏体, 发育了枕状构造、球形风化和柱状节理等玄武岩喷发等特征;后者穿插于韧性剪切带中碳酸盐质糜棱岩化中。 它们的常量组分变化较大:不包括 SiO2 外其它 9 种常量组分的含量为 36.3%~45.3%, 全碱 (Na2O+K2O)为 3.83%~7.16%;TiO2 含量较低, 为 0.63%~1.89%;MgO 为 3.72%~6.74%;前者中的常量组分、微量元素 Sr 、Ta、Nb、Ti、Yb、Ni、Cu、Zn、Y 含量明显高于后者对应值, 但大离子亲石、造岩元素中 Cs、Rb 等元素、La/Nb、K/T 元素比相对较低。 相比于原始地幔, 两者均相对富集造岩元素 Li、Rb、Ba、Ga、Sr 和稀有元素 Nb、Ta, 轻稀土中等富集;相对亏损铁族元素 Cr、Co 及 Mo、Pb、Bi、U 等;前者 ΣREE 为 227.72×10-6~426.32×10-6 、L/H = 2.51~2.61、δEu = 0.48~0.52、δCe = 0.56;后者的 ΣREE 为 142.37×10-6 ~187.92×10-6 、L/H = 2.34~3.99、δEu = 0.63~0.84、δCe = 0.52~0.54;综合判识表明, 前者主要来自于未混染或较弱混染的幔源、发育于新元古(878~808.6 Ma)板内伸展的构造环境, 变质和残留核锆石谐和年龄为 2 090 Ma, 记录了早元古的联合大陆的形成时代, 蚀变锆石 455.4±10.8 Ma 代表了加里东中晚期的岩浆热事件;后者岩浆锆石的 U-Pb 年龄为晚奥陶世 478±48 Ma, 发育于弧后盆地、与韧性剪切带有关的加里东中晚期岩浆活动。  相似文献   

16.
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).  相似文献   

17.
We present new concentration data for twenty four lithophile trace elements in NIST certified reference material glasses SRM 610-SRM 611 in support of their use in microanalytical techniques. The data were obtained by solution ICP-MS and isotope dilution TIMS analysis of two different sample wafers. An overall assessment of these new results, also taking into account ion probe studies that have been published in the literature, shows that these wafers can be considered to be homogeneous. Therefore, individually analysed wafers are believed to be representative of the entire batch of the SRM 610-611 glasses. Possible exceptions are the alkali metals (and a few volatile or non-lithophile trace elements). The analysed concentrations range between 370 μg g−1 (Cs) and 500 μg g−1 (Sr) and agree well with published values. On the basis of our new data and data recently published in the literature we propose "preferred average" values for the elements studied. These values are, within a few percent, identical to those proposed by other workers.  相似文献   

18.
We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g−1), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g−1), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g−1). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.  相似文献   

19.
流域上游基岩与下游冲积平原土壤化学组成的对比   总被引:2,自引:0,他引:2  
迟清华  马生明 《地质通报》2008,27(2):188-195
对海河水系流域、鄱阳湖水系流域上游的基岩与下游的冲积平原土壤之间化学组成的对比研究显示,下游冲积物土壤的化学组成明显地受源岩成分、形成过程和形成环境的影响。流域上游基岩的一些特征元素在冲积物土壤中被明显地继承,如海河流域基岩和土壤中的CO2、CaO、MgO、FeO、Sr,鄱阳湖流域基岩和土壤中的W、Sn、Bi、U、Th、Pb、Rb、Tl、As、Sb、Se、Hg、Nb、Ta、Hf、B、Be、Ge、Pt、Pd、Y。受形成过程和形成环境的影响,处于暖温带半湿润季风气候下的海河流域冲积平原土壤以极富集CO2、CaO、Na2O、Cl,显著富集MgO、FeO、Sr,富集P、S为特征;而处于亚热带湿润季风气候下的鄱阳湖流域冲积平原土壤则以显著富集Hg、Se和富集Al2O3、Fe2O3H2O^+、W、Sn、Bi、Mo、U、Th、Pb、Rb、Cs、Tl、Li、Be、B、Ga、Ge、Nb、Ta、Zr、Hf、As、Sb、Co、Cr、Ti、V、Zn、Pt、Pd、REE、Y为特征。无论是海河流域还是鄱阳湖流域的冲积平原土壤,均富集As、Sb、Hg、B、Cl、W、Sn、Bi、Pb、Se、Ge、Li、Cs、Cu、Au、Fe2O3、V、Cr、Ni、Zr、Hf、Y。  相似文献   

20.
National Institute of Science and Technology (NIST) silicate glass SRM 610 is widely used as a certified reference material for various micro-analytical techniques such as SIMS or laser ablation ICP-MS. SRM 610 has been nominally doped with sixty one trace elements at the 500 μg g−1 level, but certified concentration data exist for only a few of these elements. This study reports concentration data for fifty nine trace elements obtained by ICP-MS, SSMS, LIMS, TIMS, INAA, AAS, and PIXE analyses of two different SRM 610 wafers. Most elements fall within a 10% band around a median value of about 440 μg g−1. The REE concentrations are shown to be constant to 3% (1 σ), thus emphasizing the value of SRM 610 as a reference material for REE analyses.
Comparison of our values with published data suggests that different SRM 610 wafers are, within errors, chemically identical for most elements. Exceptions to this general rule appear to be restricted to elements which were partly lost during the production of the glass, e.g. Ag and Br. On the basis of six independent determinations of Rb concentrations, which are systematically lower by a few percent than the reported NIST value, we argue that the certified Rb concentration may not be representative for all distributed SRM 610 wafers.  相似文献   

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