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1.
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   

2.
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   

3.
The Ca isotopic composition of modern seawater has been determined using a 43Ca-48Ca double spike, which was calibrated using a 42Ca/44Ca seawater ratio of 0.30587 ± 0.00026. This ratio was determined from a total evaporation experiment in which the ion beam was measured from the beginning to the end of the emission. With integration of the peak intensities, the fractionation effects can be minimised, since total evaporation of the reservoir cancels out the effect of vapour enrichment in the light isotopes. This experiment avoids the gravimetric uncertainty inherent in the double spike calibration. This calibration allows the precise redetermination of the seawater isotopic composition of Ca. A mean 40Ca/44Ca ratio for two Atlantic water samples of 45.143 (2smean= 0.003) was found. The good reproducibility of the Ca isotope ratios in present seawater and the very strong isotopic homogeneity of Ca in the oceans illustrate the advantage of using seawater as the common standard, with the advantage of decreasing interlaboratory bias.  相似文献   

4.
Abstract: Carbonate rocks of Cambrian (18 samples) and lower-middle Ordovician (11 samples) ages from South Korea were analyzed for sulfur contents of structurally substituted sulfate (SSS) and sulfides and their δ34S values. The δ34S values of SSS ranging from +25.9 to +45.2 permil, are averaged as +33.6 and +33.5 permil for the Cambrian and Ordovician rocks, respectively, which indicate high δ34S values of the Cambro-Ordovician seawater. The SSS contents in the carbonate rocks are low being 2.9 to 17.3 ppm S (averaged as 7.0 ppm S). Sulfide sulfur, on the contrary, is much abundant containing 3 to 1,880 ppm S and the δ34S values range widely between –17.6 and +31.1 permil. Sulfide sulfur of the studied rocks excluding impure carbonates has an average content of 187 ppm S and δ34S value of +12.8 permil (n=24). The estimated δ34S (sulfate–sulfide) values, which range from 13.8 to 25.4 permil in general with a few exceptions from 36.5 up to 52.3 permil for some impure carbonates, may provide evidence for the persistent oceanic anoxia with its temporary recovery during the Cambro-Ordovician time.
The SSS and sulfide sulfurs have often higher δ34S values than the Mesozoic-Cenozoic ore sulfur (Ishihara et al., 2000). Since carbonate rocks are very reactive with circulating hydrothermal ore solution, high δ34S values of the Korean ore deposits might be caused to some extent by 34S enrichment from the host carbonates, resulting in the low SSS contents observed.  相似文献   

5.
Abstract: In order to know the cause of the high δ34S values of the Korean ore deposits (Ishihara et al., 2000), Geumseong molybdenum skarn deposit and related Jurassic granitoids and Cambro-Ordovician carbonates were selected for the δ34S analyses. Two sulfide samples occurring in hydrothermal veins in fresh granitoids quarry at Songhaksan yielded δ34S values of +6.9 and +8.8 permil. These are slightly higher than +5.3 permil δ34S of the averaged rock sulfides for the Jurassic Daebo granitoids. Pyrite and molybdenite from the Geumseong deposit vary from +8.6 to +11.5 permil (average + 10.7 permil). The intruded carbonates contain very low amount of SSS (structurally substituted sulfate) as 2.9 to 8.1 ppm with high δ34S values between +28.8 and + 40.0 permil, and sulfides sulfur of 52 to 779 ppm with variable δ34S values between +3.2 and +22.5 per–mil. It is concluded that sulfur of the host carbonates was extracted and migrated into the skarn deposit at the time of the granitoid intrusion and the related hydrothermal convection, on the basis of the location of the skarn deposit occurring between the carbonates and Jurassic granitoids, and of very low contents of SSS sulfur in the carbonates. A part of SSS possibly contaminated into the Jurassic granite.  相似文献   

6.
Expanded sedimentary records from the Tethys reveal unique faunal and isotopic changes across the Palaeocene-Eocene (P-E) transition. Unlike in the open oceans, the Tethys exhibits a gradual decrease of 1.5% in δ13C values prior to the rapid δ13C excursion. Associated with the 613C excursion is a decrease in calcite burial, increase in detrital content and appearance of a unique opportunistic planktic foraminifera1 assemblage (e.g. compressed acarininids). The existence of a prelude decrease in δ13C values in the Tethys suggests that the P-E δ13C excursion may have occurred in two steps and over a few hundred thousand years, rather than as one step over a few thousand years as previously suggested. This slower excursion rate is readily explained by changing organic carbon weathering or burial rates and avoids the need of invoking ad hoc scenarios.  相似文献   

7.
Abstract: Interstitial water expelled from gas hydrate-bearing and -free sediments in the Nankai Trough are analyzed in terms of Cl-, SO42-, δ18O and δD. The baselines for the Cl- concentration and δ18O value are close to seawater values (530 mM and 0%), indicating that the interstitial water is of seawater origin. The δD values decrease with depth, implying isotopic exchange of hydrogen between upwelling biogenic methane depleted in D and interstitial water. The Cl- concentrations in gas hydrate-bearing sediments are anomalously low, while the δ18O and δD values are both high, suggesting that the water forming these gas hydrates was poor in Cl- and enriched in 18O and D during gas hydrate formation. Calculation of the gas hydrate saturations using Cl "and δ18O anomalies gives results of up to 80 % in sand, and shows that the δ18O baseline is not consistent with the Cl" baseline. The δ18O baseline increases by +1% in gas hydrate-free clay and silt. This is considered to be caused by clustering of water molecules after gas hydrate dissociation in response to the upward migration of the base of gas hydrate stability, as indicated by the presence of a double bottom-simulating reflector at this site. The water clusters enriched in 18O are responsible for the increase in the δ18O baseline with normal Cl". The abrupt shallowing of the base of gas hydrate stability may induce the dissociation of gas hydrates and the accumulation of gases in the new stability zone, representing a geological process that increases gas hydrate saturation.  相似文献   

8.
ABSTRACT
The mineralogy and isotope geochemistry of carbonate minerals in the Coorong area are determined by the water chemistry of different depositional environments ranging from seawater to evaporitically modified continental water. The different isotopic compositions of coexisting calcite and dolomite suggest that each of the above two minerals was formed from water of composition and origin unique to that specific mineral. In addition, the dolomite was not formed by simple solid state cation exchange.
The occurrence of two types of dolomite was shown by isotope analysis and SEM observations. The dolomite, which is isotopically light (δ13C = -1 to -2% 0 ; δ18O=+3 to +5%0) and of fine grain size (˜ 0·5 μm) probably precipitated under the influence of evaporitically modified continental water. Coarser grained dolomite (up to 4 μm) is isotopically heavier (δ13C=+3 to +4%0; δ18O=+5 to + 6%0) contains Mg in excess of Ca and was formed in or close to equilibrium with atmospheric CO2 probably by the dolomitization of aragonite.  相似文献   

9.
ABSTRACT The carbon-isotope signature of terrestrial organic matter (OM) offers a valuable tool to develop stratigraphic correlations for near-shore deposits. A mid-Cretaceous coastal succession of the western Algarve Basin, Portugal, displays a marked negative δ13C excursion ranging from − 21.2‰ to − 27.8‰ in the Early Aptian followed by two shifts towards higher values (up to − 19.3‰) during the Early and Late Aptian, respectively. The dominance of cuticle and leaf debris in the bulk OM fraction is confirmed by optical studies, Rock-Eval pyrolysis and by comparison with the δ13C signature of four different types of fossilized land-plant particles. Correlation of two terrestrial δ13Cbulk OM records from different study sites leads to a significant enhancement of the intrabasinal stratigraphic correlation within the Algarve Basin. Three prominent excursions in the Portuguese records can be correlated with existing δ13C curves from pelagic and terrestrial environments. The general carbon-isotope pattern is superimposed by small-scale fluctuations which can be explained by compositional variations within the OM.  相似文献   

10.
Abstract. The Onsen site is an active submarine hydrothermal system hosted by the Desmos caldera in the Eastern Manus Basin, Papua New Guinea. The hydrothermal fluid is very acidic (pH=1.5) and abundant native sulfur is deposited around the vent. The δ34S values of native sulfur range from -6.5 to -9.3 %o. δ34S values of H2S and SO4 in the hydrothermal fluid are -4.3 to -9.9 %o and +18.6 to +20.0 %o, respectively. These δ34S values are significantly lower than those of the other hydrothermal systems so far reported. These low δ34S values and the acidic nature of the vent fluids suggest that volcanic SO2 gas plays an important role on the sulfur isotope systematic of the Onsen hydrothermal system. Relationship among the δ34S values of S-bearing species can be successively explained by the model based on the disproportionation reaction starting from the volcanic SO2 gas. The predicted δ34S values of SO2 agree with the measured whole rock δ34S values. δD and δ18O values of clay minerals separated from the altered rock samples also suggest the contribution of the magmatic fluid to the hydrothermal system. Present stable isotopic study strongly suggests that the Onsen hydrothermal site in the Desmos caldera is a magmatic submarine hydrothermal system.  相似文献   

11.
Abstract. Carboniferous-Permian limestones of the Akiyoshi Plateau, in the Inner Zone of southwestern Japan, are composed of essentially pure calcium carbonate containing only small amounts of other elements, and they are accompanied by marble and copper skarn deposits near the contact with late Cretaceous granitoids. The δ18O values of the Akiyoshi limestones range widely from 7.6 to 28.3% and are mostly lower than those of other areas of the same age (23–29%), whereas the differences among the δ13C values are small. The δ18O values are negatively correlated with Mn and Fe contents. Samples with high δ18O (>25%) and δ13C (>2%) values do not contain Fe, Zn, or Pb, but those with low δ18O values tend to be rich in these elements, indicating that these elements were introduced by interaction with H2O dominant fluids, possibly of magmatic origin. Potential scores for evaluating the degree of interaction with hydro thermal fluids were calculated for δ18O, δ13C, Fe, Mn, Zn, Pb, and Sr. Higher scores implying much hydrothermal interaction were evident in the Mt. Hananoyama area, where there are many skarn deposits, and along faults oriented mainly NNW-SSE. Therefore, these are promising areas for exploring for blind deposits. It is likely that the hydrothermal fluid traveled through the limestones along fractures at the time of the granitic intrusions. However, the potential scores here are much smaller than those in the Pb-Zn mineralized area of the Kamioka mine, so more detailed petrological and mineralogical investigations are necessary.  相似文献   

12.
C.J. Eastoe  & T. Peryt 《地学学报》1999,11(2-3):118-131
Routine trace-element geochemistry suggests that components in putative marine halite evaporites may be partly of nonmarine origin, but such interpretations are commonly ambiguous. Stable chlorine isotopes may provide a less-ambiguous marker of chloride origin where δ37Cl departs from the range predicted for evaporite formation from seawater. Bedded halite with primary sedimentary textures preserves original δ37Cl values. Measurable change in δ37Cl can be generated by incongruent dissolution of halite, but only if less than half the original halite remains. Badenian (middle Miocene) halite from the Forecarpathian and from the East Slovakian and Transcarpathian basins has a δ37Cl range of – 0.2 to 0.8‰. Two phenomena cannot be explained by simple evaporation of 0.0‰ seawater. At Wieliczka, the Shaft Salt has distinctive δ37Cl values (– 0.2 to 0.0‰) relative to neighbouring salt beds (0.2 to  0.6‰), requiring a large, abrupt input of brine with negative δ37Cl. Halite with high (0.6 – 0.8‰) δ37Cl near the base of the East Slovakian and Transcarpathian evaporites requires a large input of chloride with positive δ37Cl into the basins. Expulsion of basin brine with non-0‰δ37Cl into the evaporite basins may account for the nonmarine chloride sources.  相似文献   

13.
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   

14.
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   

15.
Carbon isotope measurements carried out on 201 carbonate samples from the early Proterozoic of the Kola Peninsula, N. Karelia and Norway yield δ13C (PDB) spanning - 20.5% to + 11%. A general δ13C secular trend shows that prior to 2.33 Ga values are typically 'normal' marine, averaging around - 3%0. Between 2.33 and 2.06 Ga, in Jatulian time, there follows a rapid excursion to positive δ13C of around + 6%. Post-Jatulian time is characterized by δ13C of sedimentary carbonates fluctuating between - 5% and +3%; also it is remarkable for the first pronounced development of diagenetic carbonates, which have δ13C between - 14 % and - 6% . The c. 6% positive δ13C shift with a duration of about 270 Myr coincides with a maximum in the diversity and abundance of stromatolites, and with widespread development of 'red beds', but does not coincide with the maximum of buried Corg mass. The Fennoscandian Shield represents the largest isotoically anomalous carbonate province yet reported, and the positive δ13C excursion together with a series of major global palaeoenviromental changes seems to be more intense than the Precambrian/Cambrian transition events. However, it is still not clear what kind of mechanism this phenomenon could be attributed to. An increase of the 'Ronov ratio', and/or 'Broecker ratio' and other possible models are discussed as the target for future investigations.  相似文献   

16.
The carbon (δ13 C) and oxygen (δ18O) isotopic composistion in mollusc shells in mainly determined by the isotopic composition of water and dissolved bicarbonate. The δ18O values of water show a good correlation with the salinity of the Baltic. This correlation served as a basis for reconstructing palaeosalinity and for stratifying the marine sediments according to the δ18O values of the carbonate skeletons of subfossil shells. The δ13C values in shells are mainly determined by the isotopic composition of land-originating bicarbonate, especially in the carbonate skeleton of Lymnaea balthica , which inhabits the immediate coastal zone. According to the δ18O data, salinity in the investigated area (the coastal area of W and NW Estonia) was highest (about 9–11%) during the Littorina stage. The Limnae a stage had, in general, a salinity similar to the contemporary one, but during some phases possibly exceeding it by 2–3%.  相似文献   

17.
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   

18.
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   

19.
A Barremian to Albian succession on Mount Kanala, part of a Tethyan isolated carbonate platform, was investigated for its δ13C variations. The limestone sequence is composed of a series of peritidal shallowing-upward cycles with clear petrographic evidence for strong early diagenetic overprinting related to repeated subaerial exposure. Despite significant impact of diagenesis, the observed changes in δ13C can be very well correlated with deep-water sections from different ocean basins and shallow water carbonate platforms in the Middle East. This lends further support to the applicability of δ13C variations for stratigraphic purposes in shallow-water limestones. Using the δ13C signal, time resolution in Lower Cretaceous platform carbonates can be significantly increased, independent of bio-zonations often hampered by ecological variability.
Cyclostratigraphic analysis of the Aptian part of the section shows that strong positive excursions of the cumulative departure from mean cycle thickness of the peritidal shallowing-upward cycles coincide with global positive δ13C excursions. This, and the fact that positive shifts in the δ13C record are preserved within shallow water limestones, provide evidence that black-shale accumulation in the ocean basins occurred during sea-level rise and flooding of platform tops. Integration of carbon-isotope-, cyclo- and sequence-stratigraphic results from different carbonate platforms indicate that strong positive global δ13C shifts and concurrent organic-carbon burial during black-shale deposition are ultimately caused by rapid rises of eustatic sea level. Hence, the rate of change of eustatic sea level is considered to play a crucial role in black-shale accumulation in the global ocean basins during the Cretaceous.  相似文献   

20.
Two sections of the Upper Cenomanian and Lower Turonian in central and south-east Poland were investigated for foraminifers, CaCO3content, carbon content insoluble in HCl (Corg) and in the carbonates (Ccarb), carbon and oxygen isotopic composition of bulk-rock carbonates and elemental abundances. The Cenomanian/Turonian boundary interval is characterized by the appearance of more marly facies, a δ13C and δ18O stable isotope anomaly, a considerable increase in Corg content and decrease in Ccarb content and substantial changes in the foraminiferal assemblages. A major carbon stable isotope excursion with a shift of +2 (PDB) occurs in the lowermost Whiteinella archaeocretacea Zone. The late Cenomanian δ13C anomaly is associated with heavy δ18O values. The peak value of δ13C corresponds to the minima in P/B ratio and in diversity of foraminiferal assemblages. A late Cenomanian anoxic event is thought to be responsible for changes in foraminiferal assemblages. However, elemental abundance analyses do not show changes in the concentrations of trace elements. This may be explained by the long distance between studied area and a source of enrichment which was probably located in the western hemisphere.  相似文献   

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