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1.
Application of Laser Ablation ICP-MS to U-Th-Pb Dating of Monazite   总被引：2，自引：1，他引：2  
Recent advances in laser ablation ICP-MS techniques allow accurate U-Th-Pb age dating of monazites that are as young as several tens of million years to a precision better than 2%. Accuracy of the age determinations has been improved by true real-time mass bias correction via nebulisation of a solution containing enriched 233U and natural Tl isotopes. The Tl-U tracer solution eliminates possible effects of variable sample matrices on the precision and accuracy of measured isotopic ratios. Mass bias corrections based on measured 205Tl/233U ratios in the tracer solution allow direct measurement of 235U in monazite. Combined with high-sensitivity laser ablation ICP-MS measurements, direct measurement of 235U particularly improves the precision of U-Pb dating of young monazites. Correction for laser-induced Pb/U and Pb/Th elemental fractionation is based on a mathematical treatment of time resolved count-rate data that is independent of laser ablation characteristics, does not require external standardisation and allows variable laser pit size or raster patterns for each measurement. The new procedures make the LA ICP-MS technique more flexible for in situ U-Th-Pb analysis.  相似文献   

2.
A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a 205pb-204pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a 207Pb-204Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 μg g−1 Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the "initial" Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of 205pb-204pb, 230Th and 235U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions.  相似文献   

3.
Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a microanalytical tool especially suitable for providing fast and precise U-Pb geochronological results on zircon grains. A new 193 nm excimer laser adapted to a micromachining workstation, equipped with a newly designed two-volume ablation cell and coupled with a quadrupole ICP-MS, is presented here. The system was tuned routinely to achieve sensitivities in the range of 3000 cps/μg g−1 for 238U (< 2% RSD), with a 34 μm spot size, at 5 Hz and ∼ 8 J cm−2, while ablating the NIST SRM 612 glass reference material. The system was capable of providing fast (< 1.5 minutes each analysis) and precise (generally < 1.5% 1s errors) 206Pb/238U zircon ages. The ages of widely used reference material zircons (Plesovice, 337 Ma; Temora, 416 Ma; R33, 418 Ma; Sri Lanka, 564 Ma; 91500, 1065 Ma) could be precisely matched, with an accuracy on isotopic ratios that ranged from ∼ 2 to ∼ 6%, depending on the homogeneity of the natural reference materials.  相似文献   

4.
This paper reports an investigation into the suitability of the neutron-activation method, by use of the reaction 238 U(n,γ) 239 U with detection of the gamma-rays from the daughter 239 Np, for the determination of uranium in 10 proposed reference materials. 182 Ta was used to monitor the neutron flux. The precision of measurement varied from 0.92 to 2.7 per cent. Results compare favourably with those obtained by other analytical procedures, and show that this established method can be used to yield useful and independent results in the preparation of uranium reference materials.  相似文献   

5.
New analyses have been performed in order to enhance the data-set on the independent ages of four glasses that have been proposed as reference materials for fission-track dating. The results are as follows. Moldavite - repeated 40Ar/39Ar age determinations on samples from deposits from Bohemia and Moravia yielded an average of 14.34 ± 0.08 Ma. This datum agrees with other recent determinations and is significantly younger than the 40Ar/39Ar age of 15.21 ± 0.15 Ma determined in the early 1980s. Macusanite (Peru) -four K-Ar ages ranging from 5.44 ± 0.06 to 5.72 ± 0.12 Ma have been published previously. New 40Ar/39Ar ages gave an average of 5.12 ± 0.04 Ma. Plateau fission-track ages determined using the IRMM-540 certified glass and U and Th thin films for neutron fluence measurements agree better with these new 40Ar/39Ar ages than the previously published ages. Roccastrada glass (Italy) - a new 40Ar/39Ar age, 2.45 ± 0.04 Ma, is consistent with previous determinations. The Quiron obsidian (Argentina) is a recently discovered glass that has been proposed as an additional reference material for its high spontaneous track density (around 100 000 cm-2). Defects that might produce "spurious" tracks are virtually absent. An independent 40Ar/39Ar age of 8.77 ± 0.09 Ma was determined and is recommended for this glass. We believe that these materials, which will be distributed upon request to fission-track groups, will be very useful for testing system calibrations and experimental procedures.  相似文献   

6.
An igneous zircon reference material (OG1) was characterised for U-Pb isotopes by ID-TIMS, and utilised to evaluate SIMS (SHRIMP) instrumental mass fractionation (IMF) of radiogenic Pb isotopes (207Pb*/206Pb*). The TIMS 207Pb*/206Pb* reference value for OG1 was 0.29907 ± 0.00011 (95% confidence limit), 3465.4 ± 0.6 Ma. The high 207Pb* (∼ 30 μg g−1), negligible common Pb, and isotopic homogeneity permitted precise (± 1–2‰) 207Pb*/206Pb* measurements within the analytical sessions. External reproducibility of mean 207Pb*/206Pb* ratios between sessions was demonstrated for one instrument, yielding a mean IMF of +0.87 ± 0.49‰. The mean 207Pb*/206Pb* ratios between instruments were dispersed beyond uncertainties, with session IMF values from +3.6 ± 1.7‰ to −2.4 ± 1.3‰, and a grand mean IMF value (twenty-six sessions) of +0.70 ± 0.52‰, indicating a tendency towards elevated 207Pb*/206Pb*. The specific causes of variability in IMF are unclear, but generally reflect subtle differences in analytical conditions. The common practice in SIMS of assuming that IMF for Pb+ is insignificant could result in systematic age biases and underestimated uncertainties, of critical importance for precise correlation of Precambrian events. Nevertheless, a zircon RM such as OG1 can be readily incorporated into routine dating to improve 207Pb*/206Pb* accuracy and external reproducibility.  相似文献   

7.
We report silicon isotopic determinations for USGS rock reference materials BHVO-1 and BHVO-2 using a Nu Plasma multi-collector (MC)-ICP-MS, upgraded with a new adjustable entrance slit, to obtain medium resolution, as well as a stronger primary pump and newly designed sampler and skimmer cones ("B" cones). These settings, combined with the use of collector slits, allowed a resolution to be reached that was sufficient to overcome the 14N16O and 14N2 interferences overlying the 30Si and the 28Si peaks, respectively, in an earlier set-up. This enabled accurate measurement of both δ30Si and δ29Si. The δ value is expressed in per mil variation relative to the NBS 28 quartz reference material. Based on data acquired from numerous sessions spread over a period of six months, we propose a recommended average δ30Si of −0.33 ± 0.05‰ and −0.29 ± 0.11‰ (2se) for BHVO-1 and BHVO-2, respectively. Our BHVO grand mean silicon isotope composition (δ30Si =−0.31 ± 0.06‰) is significantly more negative than the only published value for BHVO-2, but is in very good agreement with the recently established average value of ocean island basalts (OIB), confirming the conclusion that the OIB reservoir has a distinct isotopic composition from the solar reservoir as sampled by chondrites.  相似文献   

8.
In this study we evaluated the capability of a 213 nm laser ablation system coupled to a quadrupole-based ICP-MS in delivering accurate and precise U-Pb ages on zircons and monazites. Four zircon samples ( ca. 50 Ma to ca. 600 Ma) and four monazite samples ( ca. 30 Ma to ca. 1390 Ma) of known ages were analysed utilising laser ablation pits with diameters of 20 μm and 60 μm. Instrument mass bias and laser induced time-dependent elemental fractionation were corrected for by calibration against a matrix-matched reference material. Tera-Wasserburg plots of the calculated U-Pb data were employed to assess, and correct for, common Pb contributions. The results indicated that the LA-ICP-MS technique employed in this study allowed precise and accurate U-Pb isotope dating of zircon and monazite on sample areas 20 μm in diameter. At this spot size, the precisions achieved for single spot 206Pb/238U ages, were better than 5% (2s) for monazites and zircons with ages down to 30 Ma and 50 Ma, respectively. The precisions reported are comparable to those generally reported in SIMS and LA-MC-ICP-MS U-Pb isotope determinations.  相似文献   

9.
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.  相似文献   

10.
The δ13Ccarb and 87Sr/86Sr secular variations in Neoproteozoic seawater have been used for the purpose of 'isotope stratigraphy' but there are a number of problems that can preclude its routine use. In particular, it cannot be used with confidence for 'blind dating'. The compilation of isotopic data on carbonate rocks reveals a high level of inconsistency between various carbon isotope age curves constructed for Neoproteozoic seawater, caused by a relatively high frequency of both global and local δ13Ccarb fluctuations combined with few reliable age determinations. Further complication is caused by the unresolved problem as to whether two or four glaciations, and associated negative δ13Ccarb excursions, can be reliably documented. Carbon isotope stratigraphy cannot be used alone for geological correlation and 'blind dating'. Strontium isotope stratigraphy is a more reliable and precise tool for stratigraphic correlations and indirect age determinations. Combining strontium and carbon isotope stratigraphy, several discrete ages within the 590–544 Myr interval, and two age-groups at 660–610 and 740–690 Myr can be resolved.  相似文献   

11.
Calcium Isotopic Composition of Various Reference Materials and Seawater   总被引：1，自引：0，他引：1  
A compilation of δ44/40Ca (δ44/40Ca) data sets of different calcium reference materials is presented, based on measurements in three different laboratories (Institute of Geological Sciences, Bern; Centre de Géochimie de la Surface, Strasbourg; GEOMAR, Kiel) to support the establishment of a calcium isotope reference standard. Samples include a series of international and internal Ca reference materials, including NIST SRM 915a, seawater, two calcium carbonates and a CaF2 reference sample. The deviations in δ44/40Ca for selected pairs of reference samples have been defined and are consistent within statistical uncertainties in all three laboratories. Emphasis has been placed on characterising both NIST SRM 915a as an internationally available high purity Ca reference sample and seawater as representative of an important and widely available geological reservoir. The difference between δ44/40Ca of NIST SRM 915a and seawater is defined as -1.88 O.O4%o (δ44/42CaNISTSRM915a/Sw= -0.94 0.07%o). The conversion of values referenced to NIST SRM 915a to seawater can be described by the simplified equation δ44/40CaSa/Sw=δ44/40CaSa/NIST SRM 915a - 1.88 (δ44/42CaSa/Sw=δ44/42CaSa/NIST SRM 915a - 0.94). We propose the use of NIST SRM 915a as general Ca isotope reference standard, with seawater being defined as the major reservoir with respect to oceanographic studies.  相似文献   

12.
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   

13.
In this study, the Cd isotopic composition of various geological reference materials and anthropogenic samples was investigated. The measurements were made by multicollector ICP-MS and instrumental mass fractionation was controlled using a "sample-standard bracketing" technique. Cadmium isotopic data are reported relative to an internal Cd solution (Cd Spex) and expressed as the 114 Cd/110Cd delta value. Two other Cd solutions (Prolabo and JMC) were analysed and yielded the same 0% delta value. A fractionated Cd metal sample (Münster Cd) was used as a secondary reference material for Cd isotopic measurements and we obtained a 114 Cd/110 Cd delta value of 4.48% relative to Cd Spex solution. As opposed to multi-stage Cd purification previously published in the literature, a new one step anionic exchange purification using dilute HCl for the analysis of Cd isotopes in geological samples was developed. This method enabled a high recovery (> 95%) and effective separation of the sample matrix to be achieved. The long-term external reproducibility was evaluated at 0.12% (2 standard deviations) for the 114 Cd/110Cd ratio, based on reference solutions and replicated measurements of samples over one year. The variation of Cd isotopic composition of natural terrestrial samples is restricted to a small range of 0.4%, which is similar to previously reported results. In contrast, large variations of Cd isotopic composition were found for anthropogenic samples with values as low as −0.64% for a dust sample issued from a lead smelter and values as high as +0.50% for NIST SRM 2711 (metal-rich soil). These variations are 10 times larger than the reproducibility and suggest that Cd isotopes can be useful as tracers of anthropogenic sources of Cd in the environment.  相似文献   

14.
Notations for Cd stable isotope compositions and the use of reference materials are discussed. It is proposed that Cd stable isotope data should be reported as variations of the 114Cd/110Cd ratio/ using either the δ114/110Cd or ε114/110Cd notations. Future publications should report results for BAM-1012 Cd, the only currently available international Cd isotope reference material. It is also recommended that "Münster Cd" and a range of specified geological reference materials are used as additional reference materials. The final choice of a primary "zero-delta" reference standard remains the most important outstanding question.  相似文献   

15.
This paper presents an adapted anion exchange column chemistry protocol which allowed separation of high-purity fractions of Cu and Zn from geological materials. Isobaric and non-spectral interferences were virtually eliminated for consequent multiple-collector ICP-MS analysis of the isotopic composition of these metals. The procedure achieved ∼ 100% recoveries, thus ensuring the absence of column-induced isotopic fractionation. By employing these techniques, we report isotopic analyses for Cu and Zn from five geological reference materials: BCR-027 blende ore (BCR), δ65Cu = 0.52 ± 0.15‰ (n = 10) and δ66Zn = 0.33 ± 0.07‰ (n = 8); BCR-030 calcined calamine ore (BCR), δ66Zn = -0.06 ± 0.09‰ (n = 8); BCR-1 basalt (USGS), δ66Zn = 0.29 ± 0.12‰ (n = 8); NOD-P-1 manganese nodule (USGS), δ65Cu = 0.46 ± 0.08‰ (n = 10) and δ66Zn = 0.78 ± 0.09‰ (n = 9); SU-1 Cu-Co ore (CCRMP), δ65Cu = -0.018 ± 0.08‰ (n = 10) and δ66Zn = 0.13 ± 0.17‰ (n = 6). All uncertainties are ± 2s; copper isotope ratios are reported relative to NIST SRM-976, and zinc isotope ratios relative to the Lyon-group Johnson Matthey metal (batch 3-0749 L) solution, JMC Zn. These values agree well with the limited data previously published, and with results reported for similar natural sample types. Samples were measured using a GVi IsoProbe MC-ICP-MS, based at the Natural History Museum, London. Long-term measurement reproducibility has been assessed by repeat analyses of both single element and complex matrix samples, and was commonly better than ± 0.07‰ for both δ66Zn and δ65Cu.  相似文献   

16.
During the last few years, a remarkable anomaly between 238U and 234U activities has been observed in the top layers of the coastal sediments along the western region of the Indian sub-continent. Sediment samples from Bombay (19°N, 73°E) to Kottilppad (8°N, 77°E) were leached with saturated ammonium carbonate solution to extract uranium isotopes from the surface layers of the sediment particles without attacking the mineral cores. The 234U/238U activity ratios in these leachates are in the range of 1.12–1.14 while 235U/238U activity ratio is 0.046 which is the same as for other natural uranium.

The surface organic matter from the sediment particles was removed by treatment with hydrogen peroxide in presence of 0.05 M hydrochloric acid. 234U/238U and 235u/238U activity ratios in the extract and the residues were determined.

It is observed that disequilibrium between 238U and 234U exists only on the surface of sediment particles. 234U/238U on the surface of the sediment particles is the same as in the ambient water and as the surface organic matter is removed from the particle surface, the cores show equilibrium activities.  相似文献   


17.
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   

18.
Data from a series of extended analytical sessions using a range of different zircon reference samples have been used to investigate the periodic derivation of abnormal 207Pb/206Pb ages during microbeam analysis%For the Canberra SHRIMP II, this phenomenon probably results from the presence of a signal at mass 204 that is alien to the Pb spectrum; isotopic fractionation is unlikely to be a significant contributor. In contrast, abnormal 207Pb/206Pb ages obtained from SHRIMP I at the same research centre require a different, but as yet unknown explanation. Assessment of the reasons for atypical 207Pb/206Pb measurements and the means of correcting for them should therefore be independently assessed for individual analytical instruments. The use of reference samples with very different ages is an effective way of doing this, because older reference samples are more useful for documenting isotopic fractionation, whereas younger ones are more sensitive indicators of isobaric interference.  相似文献   

19.
ABSTRACT This work presents a detailed 87Sr/86Sr isotope curve for the interval 7.5–9.7 Ma obtained by a high-resolution analysis (sampling spacing of about 40 kyr) of an astronomically calibrated land-based sedimentary sequence exposed in the central Mediterranean area (Gibliscemi section, southern Sicily). The main aim is to verify a synchronous response of the Mediterranean seawater Sr isotope record to the oceanic forcing on the basis of multiple comparisons of the Gibliscemi record with published coeval 87Sr/86Sr curves. A good correlation with the 87Sr/86Sr data from the ODP site 926 (equatorial Atlantic ocean), considered to be the Sr chemostratigraphic reference section for the Late Miocene, and from the Pacific DSDP site 590B was registered. Conversely, the comparison of the Gibliscemi Sr isotope data with 87Sr/86Sr ratios from the coeval segment of the land-based Sardella section (eastern Mediterranean) shows important differences highlighting a local control on the seawater Sr isotope changes in semi-isolated subbasins within the Late Miocene Mediterranean.  相似文献   

20.
A proposal is made to standardise the reporting of Ca isotope data to the δ44Ca/40Ca notation (or δ44Ca/42Ca) and to adopt NIST SRM 915a as the reference standard.  相似文献   

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