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1.
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   

2.
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   

3.
A direct method for the determination of lead isotopic ratios by laser ablation-inductively coupled plasma-quadrupole mass spectrometry (LA-ICP-QMS) is presented. Samples of lake sediments were ground and pressed as pellets before being analysed. Mass bias was corrected by analysing an external calibration sample manufactured with pure silica doped with NIST SRM 981 solution. The efficiency of the mass bias correction was checked by comparing the ICP-MS data with lead isotopic ratios determined by thermal ionisation mass spectrometry (TIMS). The average long term reproducibilities were 0.40%, 0.40%, 0.20% and 0.30% (RSD) respectively for the 206Pb/204Pb, 207Pb/204Pb, 206Pb/207Pb and 208Pb/206Pb ratios. The method was applied to the study of lake sediment samples, in order to determine the amount and origin of historical contamination by lead.  相似文献   

4.
We present boron isotope and concentration data from magmatic (komatiitic to rhyolitic) and sedimentary geological silicate and artificial glass reference materials that cover a wide spectrum of boron isotope compositions and boron concentrations. Boron isotope compositions were determined by TIMS (Cs2BO2+ -graphite and BO2- method) and boron concentrations by ICP-AES. Boron concentrations ranged from 7 to 159μ g-1 and agree within 14% with published values. Based on replicate analyses of individually prepared sample aliquots an overall external reproducibility of better than 10% was determined. The obtained δ11B values ranged from -12.6 to +13.6% and were reproducible within 1.1 % (2 RSD; excluding NTIMS) on the basis of individually prepared sample aliquots. The δ11B values of JA-1 (+5.3%), JB-3 (+5.9%) and JR-2 (+2.9%) overlap the published data within analytical uncertainty. For the first time δ11B values for the TB (-12.6%) and the MPI-DING glasses GOR-128-G (+13.6%), GOR-132-G (+7.1 %) and StHs6/80-G (-4.5%) are reported. The δ11B values obtained by the Cs2BO2+ -graphite and the BO2- method as well as the majority of δ11B values obtained using different sample preparation methods agree within analytical uncertainty. Therefore, we conclude that none of these analytical methods introduce any systematic error on the obtained δ11B values.  相似文献   

5.
In 140 metres of Maastrichtian White Chalk (nannofossil chalk) exposed near Hemmoor, NW Germany, values of 87Sr/86Sr increase from 0.707760 in the Belemnella sumensis Zone (Lower Maastrichtian) at the base of the section (-54.5 m; referred to 0 m at a prominent marl, M900) to 0.707821 in the Belemnella baltica/danica Zone (Upper Maastrichtian) at the top of the section (+84.5 m). A plateau in 87Sr/86Sr occurs between -5m and +50m in the section, probably as a result of a very high rate of sedimentation in this interval. A belemnite and associated nannofossil chalk have similar 87Sr/86Sr values, suggesting that there has been little diagenetic alteration of the 87Sr/86Sr ratios in the chalk, which therefore preserves its original 87Sr/86Sr. Comparison of 87Sr/86Sr and nannofossil zonations for sequences at Bidart, France, and DSDP Sites reveals discordance and so possible diachronism of the basal boundaries of nannofossil Zones CC25B and CC25C.  相似文献   

6.
For studies of mass-dependent fractionation of calcium isotopes in natural materials, the 48Ca/42Ca ratio is a superior choice to the conventionally measured 44Ca/40Ca ratio for two important reasons. These are (1) mass-dependent fractionation can be determined free from the effects of inherited or ingrown radiogenic 40Ca and (2) this ratio increases the spread of measured isotopic masses by 50%, resulting in statistically better resolution of fractionation, assuming similar precision. A third, though strictly technical, advantage is the inherent ability of a mass spectrometer to measure ratios close to unity (48Ca/42Ca) more precisely than very small or large ratios (44Ca/40Ca). However, because of the very low natural abundance of both 48Ca and 42Ca, their ratio has been very difficult to measure, the only attempt so far being on a high mass resolution MC-ICP-MS with a precision of 0.33%. We report here determination of the 48Ca/42Ca ratio by the more commonly available and user-friendly multi-collector TIMS using a 43Ca-46Ca double-spike, with a significantly better precision of 0.18% (2s). The 48Ca/40Ca or 44Ca/40Ca ratio can also be measured in the same mass spectrometer run to provide complementary information on any radiogenic component.  相似文献   

7.
A method developed for radiochemical determination of gold in rock samples has been applied to six Bulgarian, four ZGI (GDR) and one USGS geostandards. The method is based on acid dissolution of the sample, followed by extraction of gold with copper diethyldithiocarbamate solution in CHCl3. The chemical yield was determined by using 199Au tracer. The present data are compared with published values for the ZGI and USGS samples.  相似文献   

8.
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   

9.
Artificial radionuclides (60Co, 106Ru, 134Cs and 137Cs) produced in the nuclear power plants along the Rhne valley have been detected in most of the 35 sediment samples collected from the shores of the Rhne river in southern France. In one sample traces of 241Am were found, suggesting the presence of transuranic elements. The wide use of river water for irrigation and the occasional big inundations of the Rhne have spread the artificial radionuclides over huge areas, quite far behind the river shores. Although artificial radionuclides are present in fields where food crops are collected, their activity is currently considerably lower than the activity of the natural radionuclides present in the river sediment.  相似文献   

10.
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   

11.
The fluorine concentration in seventy-one reference samples of geological interest has been determined using fast-neutron activation analysis. The reaction involved [19F(n, α) 16N] uses accelerator-derived neutrons produced by bombarding a Be target with 3 MeV deuterons. The gamma radiation associated with the decay of 16N (t1/2 = 7.13 s) is counted and for the irradiation conditions used there are no serious interferences. The advantages of this technique over other schemes of fluorine determination are its simple procedure for sample preparation, speed, high sensitivity and non-destructiveness. A comparison of the data obtained with those in the literature is highly favourable.  相似文献   

12.
We have developed a new chemical procedure for the quantitative separation of molybdenum (Mo) and rhenium (Re) from a wide variety of geological samples. A single pass anion exchange separation provided complete recovery of pure Mo and Re in a form that was ideal for subsequent isotope and abundance determination by multi-collector inductively coupled plasma-mass spectroscopy (MC-ICP-MS). An enriched 100Mo-97Mo solution, mixed with the sample before digestion, enabled natural mass-dependant isotopic fractionation of Mo to be determined with an external reproducibility of < 0.12‰ (δ98Mo/95Mo, 2 s ). Determination of the concentration of Mo and Re in the same sample was achieved by isotope dilution, with instrumental mass-fractionation of Re being corrected by the simultaneous measurement of the 191Ir/193Ir ratio. We have applied the new procedure to a variety of samples, including seawater, basalt and organic-rich mudrock. The procedure is ideally suited to palaeoredox studies requiring the precise determination of the Mo isotope composition and the Re/Mo ratio from the same sample.  相似文献   

13.
In this paper we address the question of how to determine the period of activity (sedimentation) of fossil (Holocene) fluvial systems in vertically aggrading environments. Our data base consists of almost 100 14C ages (partly AMS) from the Rhine–Meuse delta in the central Netherlands. Radiocarbon samples from the tops of lithostratigraphically correlative organic beds underneath overbank deposits (sample type 1) yield consistent ages, indicating a synchronous onset of overbank deposition over distances of at least up to 20 km along channel belts. Similarly, 14C ages from the base of organic residual channel fills (sample type 3) generally indicate a clear termination of within-channel sedimentation. In contrast, 14C ages from the base of organic beds overlying overbank deposits (sample type 2), commonly assumed to represent the end of fluvial sedimentation, show a large scatter reaching up to 1000 14C years. This setting usually produces 14C ages significantly younger than residual channels of the same fluvial system, indicating the presence of non-depositional unconformities. These usually occur on top of slightly elevated sediment bodies (especially natural levee deposits), which often contain palaeosols. Such hiatuses appear to be much more abundant than hitherto supposed. We conclude that a combination of sample types 1 and 3 generally yields a satisfactory delimitation of the period of activity of a fossil fluvial system. The problems associated with 14C samples of type 2 may also be present in coastal areas with an alternation of tidal deposits and organic beds.  相似文献   

14.
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   

15.
A selective and sensitive spectrophotometric method has been developed for determining the total amount of vanadium in carbonaceous shales (stone coal ores). The method is based on the reaction of vanadium(V) with the chromophore reagent 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) in the presence of hydrogen peroxide. In a 0.072 mol l−1 sulfuric acid medium, 5-Br-PADAP reacts with vanadium(V) to form a red-violet complex with a maximum absorption peak at 596 nm with an apparent molar absorption coefficient of the complex of 8.45 × 104 l mol−1 cm−1. Beer's law was obeyed in the range 0–25 μg vanadium in 25 ml of solution, with a correlation coefficient of 0.9995. Interferences due to various non-target ions were also investigated and high quantities of other common inorganic ions were tolerable. The method involved the dissolution of the ore sample by Na2O2 fusion, followed by filtering of the alkali solution after which Fe(III), Cu(II), Ni(II) and Co(II) etc. were effectively separated from the solution by precipitation in a NaOH solution. Selectivity was increased with the use of EDTA as a masking agent. The vanadium in ore samples was determined with a relative deviation (RSD) between 0.20 and 0.76%, and has been successfully applied to the determination of vanadium-bearing stone coal ores. The results indicated that the accuracy of 5-Br-PADAP spectrophotometry is comparable with the ICP-AES method. The characteristics of the method, i.e., simplicity, selectivity, sensitivity and rapid calibration, make it specially suitable for routine analysis.  相似文献   

16.
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   

17.
Values of δ13C obtained from conventional bulk sediment radiocarbon dates encompassing the Pleistocene Holocene boundary have been compiled and plotted against 14C age. In all. 286 lake sediment dates from southern Sweden in the range 8.000 to 13.000 BP have been evaluated. A significant decrease in δ13C values, initiated shortly before 10.000 RP and amounting to 5%, is distinguished. This change is accompanied by increased limnic productivity. decreased erosive input and increased organic carbon content of the sediments. A probable explanation for the δ13C decline in organic material is decreased importance of dissolution of silicates at the transition to the Holocene. During the Late Weichselian. extensive weathering of exposed minerogenic material with subsequent input of bicarbonate to the lake water may have caused a relative enrichment of 13C in dissolved inorganic carbon. Furthermore, the early Holocene increase in terrestrial vegetation cover probably led to an increased supply of 13C depleted carbon dioxide to the lake water by root respiration. Altered limnic vegetation, presumably towards increased production of phytoplankton. could also have contributed to the observed decreasing δ13C trend. The importance of these processes compared to other possible influencing factors. mainly endogenic carbonate production and changes in the global carbon cycle. is discussed.  相似文献   

18.
Nine stratigraphic sections, each ≈5 m thick, were sampled from the Alamogordo Member limestones of the Lake Valley Formation, Sacramento Mountains, New Mexico, USA. Four stratigraphic sections consist entirely of lime mudstone and wackestone, whereas the other five sections have a prominent layer of crinoidal packstone about 1 m thick at their base. Stable isotopic analyses reveal that the lime muds in the sections with basal packstone layers show a downward decrease in δ18O and constant δ13C values, whereas those in the sections solely composed of lime mudstone and wackestone have, in general, relatively uniform δ18O and δ13C values. The diagenesis of the Alamogordo Member limestones was previously believed to have been governed by the downward percolation of meteoric water from a regional pre-Pennsylvanian exposure surface ≈100 m above this unit. However, the uniform δ13C and downward decrease in δ18O values in the lime muds in the sections with basal packstones indicate that the meteoric water ascended within the Alamogordo Member, rather than descended from the overlying exposure surface. This indicates that the basal packstones were probably a conduit for meteoric water. This is further supported indirectly by the relatively uniform δ18O and δ13C values of the lime mud in the sections without basal packstones. The implications are that the oxygen isotopic gradients may be used to identify palaeoaquifers, flow directions within these aquifers and that meteoric diagenesis below an exposure surface could be governed by flow through a palaeoaquifer.  相似文献   

19.
Refinements have been made to achieve over 99% yield in the conversion of CO to CO2 in order to improve the reproducibility and accuracy of δ18 O measurements in sulfates. BaSO4 (10-15 mg) was mixed with an identical amount of spectrographic-grade graphite and loaded into a Pt boat. The mixture was gradually heated to 1100 °C to reduce sulfate to CO and CO2; the former gas was simultaneously converted to CO2 by a glow discharge between Pt electrodes immersed in a magnetic field (produced by a pair of external neodymium magnets). A small memory effect was noticed during the analysis (less than 0.3‰ per 10‰ difference in δ18 O between two subsequently analysed samples). The memory effect, however, was suppressed by repetitive preparation of the same specimen. CO2 produced in this way from sulfate reference samples was analysed on a dual inlet and triple collector mass spectrometer along with CO2 equilibrated with VSMOW, GISP and SLAP water reference samples. To avoid large departures of measured isotope ratios from 18O/16O of the working calibrator we used CO2 gas prepared from ocean water sulfate for this purpose. The calibrated δ18 O values (in ‰) obtained in this way for NBS-127, IAEA SO-5 and IAEA SO-6 reference materials were 8.73 ± 0.05, 12.20 ± 0.07 and -10.43 ± 0.12, respectively.  相似文献   

20.
Gustavsson, J. E. & Högberg, S. A. C.: Uranium/thorium dating of Quaternary carbonates. Boreas, Vol. 1, pp. 247–274. Oslo, 1st December, 1972.
The U/Th methods and particularly the theory of the 230Th-deficiency method are reviewed. The closed system question is discussed against the background of the growth and structure of the molluscan shells measured. The choice of the half-life value for 230Th, 75,200 years, is accounted for in a review of the five half-life determinations known to the authors. The measurement procedure starts with the mechanical and ultrasonic cleaning of the sample. Small portions are taken for X-ray analysis. The sample is then divided into two parts. One is treated chemically to separate the uraninium and the thorium, in order to determine the ratio between the activities of the uranium isotopes and to determine the content of 226Ra. The other part of the sample is used to make the total measurement on the uranium and thorium isotopes simultaneously from the same part of the sample without any chemical pretreatment.  相似文献   

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