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1.
The short residence times of Th and Pa in seawater make them very responsive to changes in the ocean environment. We use a new multi-ion-counting technique to make Th and Pa isotope measurements in seawaters from a near-shore environment in which oceanic chemical tracers are not overwhelmed by terrestrial inputs (the Bahamas). An unusual feature of the Bahamas setting is the shallow depth of water residing on the bank tops. These waters have significantly lower 232Th/230Th (∼10,000) than those immediately adjacent to the banks (24,000-31,000) and a (231Pa/230Th) near the production ratio (∼0.1). The change in 232Th/230Th and (231Pa/230Th) on the bank tops is explained by almost quantitative removal of Th and Pa by scavenging, and their replacement with a mixture of 230Th and 231Pa alpha-recoiled from the underlying carbonates, together with Th from dust dissolution. Analysis of a water profile in the Tongue of the Ocean, which separates the Great and Little Bahama Banks, allows us to trace the movement of bank-top water to depth. A distinct minimum in both 232Th/230Th (∼13,000) and (231Pa/230Th) (∼0.5) is observed at ∼430 m and is interpreted to reflect density cascading of bank-top water with entrained carbonate sediment. These results suggest that Th and Pa can be used as water-mass tracers in near-shore environments. Uranium concentration measurements on the same waters demonstrate that U is conservative across a range in salinity of 2 psu, with a concentration of 3.33 ppb (at a salinity of 35).The incorporation of U and Th isotopes into marine carbonates has also been assessed by analyzing carbonate samples from the same location as these Bahamas waters. Such incorporation is critical for U-Th geochronology. U isotope analyses demonstrate that seawater δ234U averages 146.6 and does not vary by more than 2.5%o, and that carbonates capture this value. Additional high precision measurements (≈±1%o) on modern carbonates confirm that all oceans have identical δ234U. Modern marine carbonates are shown to have 232Th/230Th ratios that reflect the local seawater in which they formed.  相似文献   

2.
Deep-sea coral has proved useful for paleoceanographic reconstructions and for documenting 14C-ages of water masses using 230Th-ages. However, for precise and accurate U-series dating, further information on coral-age structure, growth rate and diagenetic evolution is still needed. To document such processes, we used U-Th-226Ra systematics in a 40 cm diameter, Lophelia pertusa specimen collected in 1912 from the Eastern Atlantic (Sea of the Hebrides). External parts of the specimen are thought to have been alive when collected whereas more internal parts were likely dead. The “live-collected” and “dead” parts of the skeleton were sampled and analyzed for their 230Th, 232Th, 234U, 238U, 226Ra and Ba contents by thermal ionization and multicollector inductively coupled plasma mass spectrometry. 230Th/234U ratios in the most recent parts yielded ages of 86 ± 6 a and 92 ± 9 a, in agreement with the date of recovery. The older parts yielded 230Th ages ranging from 169 ± 15 to 211 ± 10 a (n = 5), but had a 31% higher U content than more recent parts of the skeleton. This raises concerns about the possibility of secondary diagenetic U uptake, although an environmentally controlled U/Ca shift between coral growth stages cannot be ruled out. 226Ra/Ba measurements were made, and model- 226Ra/Ba ages averaging 250 ± 12 yr were calculated for the older part, assuming a constant initial 226Ra/Ba ratio in bottom waters. These ages are slightly older than 230Th-ages, suggesting either that 226Ra/Ba ratios of ambient-seawater changed over time or that a diagenetic phenomenon have affected the U-series system, or both. Scanning electron microscope observations revealed bioerosion and secondary biomineralization in the older part of the coral skeleton, supporting the hypothesis that diagenetic processes may have influenced the ages obtained by the U-series toolbox. Modeled U-series ages for such an open system are discussed. However, a comparison between 14C- and 230Th-ages performed on both pristine and bioeroded parts of the coral gives coherent values (ca 450 a) for the preindustrial 14C-reservoir age of North Atlantic waters. It remains to be determined, however, whether diagenesis occurs rapidly over a short period of time, or whether it continues for longer periods. In the latter case, diagenetic processes would hamper paleoceanographic interpretations as well as the precise calculation of 14C ages of deep-water masses, based on comparative U/Th- and 14C-chronologies.  相似文献   

3.
A 230Th-234U-238U dating study on pedogenic silica-carbonate clast rinds and matrix laminae from alluvium in Crater Flat, Nevada was conducted using small-sample thermal-ionization mass spectrometry (TIMS) analyses on a large suite of samples. Though the 232Th content of these soils is not particularly low (mostly 0.1-9 ppm), the high U content of the silica component (mostly 4-26 ppm) makes them particularly suitable for 230Th/U dating on single, 10 to 200 mg totally-digested samples using TIMS. We observed that (1) both micro- (within-rind) and macro-stratigraphic (mappable deposit) order of the 230Th/U ages were preserved in all cases; (2) back-calculated initial 234U/238U fall in a restricted range (typically 1.67±0.19), so that 234U/238U ages with errors of about 100 kyr (2σ) could be reliably determined for the oldest, 400 to 1000 ka rinds; and (3) though 13 of the samples were >350 ka, only three showed evidence for an open-system history, even though the sensitivity of such old samples to isotopic disruption is very high. An attempt to use leach-residue techniques to separate pedogenic from detrital U and Th failed, yielding corrupt 230Th/U ages. We conclude that 230Th/U ages determined from totally dissolved, multiple sub-mm size subsamples provide more reliable estimates of soil chronology than methods employing larger samples, chemical enhancement of 238U/232Th, or isochrons.  相似文献   

4.
Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ13C, δ15N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ13C = −22.8 ± 1.0‰; δ15N = 5.5 ± 0.6‰). δ13C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ15N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL1, HL2, HL4, and HL5), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ13C (down to −28‰) and δ15N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL1, HL2, and with lesser extent for HL4. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL5, only the δ13C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL5 to HL1 (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ13C, increasing OC/TN and decreasing δ15N values.  相似文献   

5.
The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ34S (−38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (−38‰ to −22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ34S values (−14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ34S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The 87Sr/86Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ18O consistent with a marine environment. Its δ13C is however lower than those of marine carbonates, suggesting a contribution of 13C-depleted carbon from degradation of organic matter. δ18O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ18O values (∼+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.  相似文献   

6.
《Applied Geochemistry》2002,17(6):781-792
Samples of tuff from boreholes drilled into fault zones in the Exploratory Studies Facility (ESF) and relatively unfractured rock of the Cross Drift tunnels, at Yucca Mountain, Nevada, have been analysed by U-series methods. This work is part of a project to verify the finding of fast flow-paths through the tuff to ESF level, indicated by the presence of ‘bomb’ 36Cl in pore fluids. Secular radioactive equilibrium in the U decay series, (i.e. when the radioactivity ratios 234U/238U, 230Th /234U and 226Ra/230Th all equal 1.00) might be expected if the tuff samples have not experienced radionuclide loss due to rock-water interaction occurring within the last million years. However, most fractured and unfractured samples were found to have a small deficiency of 234U (weighted mean 234U/238U=0.95±0.01) and a small excess of 230Th (weighted mean 230Th/234U 1.10±0.02). The 226Ra/230Th ratios are close to secular equilibrium (weighted mean=0.94±0.07). These data indicate that 234U has been removed from the rock samples in the last ∼350 ka, probably by pore fluids. Within the precision of the measurement, it would appear that 226Ra has not been mobilized and removed from the tuff, although there may be some localised 226Ra redistribution as suggested by a few ratio values that are significantly different from 1.0. Because both fractured and unfractured tuffs show approximately the same deficiency of 234U, this indicates that pore fluids are moving equally through fractured and unfractured rock. More importantly, fractured rock appears not to be a dominant pathway for groundwater flow (otherwise the ratio would be more strongly affected and the Th and Ra isotopic ratios would likely also show disequilibrium). Application of a simple mass-balance model suggests that surface infiltration rate is over an order of magnitude greater than the rate indicated by other infiltration models and that residence time of pore fluids at ESF level is about 400 a. Processes of U sorption, precipitation and re-solution are believed to be occurring and would account for these anomalous results but have not been included in the model. Despite the difficulties, the U-series data suggest that fractured rock, specifically the Sundance and Drill Hole Wash faults, are not preferred flow paths for groundwater flowing through the Topopah Spring tuff and, by implication, rapid-flow, within 50 a, from the surface to the level of the ESF is improbable.  相似文献   

7.
Electron spin resonance (ESR) dating and thermal ionization mass spectrometric 230Th/234U dating was conducted on six teeth from the prehistoric site of Amud Cave. By combining the ESR and 230Th/234U analyses, we obtained burial ages for teeth in various layers of the site. Layer B1/6–7, from which the Amud I Neanderthal skeleton was recovered, is dated to 53 ± 8 ka. Layer B2/8, which yielded other important human remains including the Amud 7 skeleton, gives a mean burial age of 61 ± 9 ka. One tooth from the lowest layer (B4) yielded a date of 70 ± 11 ka, but another tooth from this layer gave an 113 ± 18 ka. Despite this discrepancy, these ages agree with previously published TL ages on heated flints for the corresponding layers. This agreement between ESR on tooth enamel and TL on burned flint is also seen at all other sites studied with both methods in Israel. © 2001 John Wiley & Sons, Inc.  相似文献   

8.
Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the 234U/238U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%).The pore water 234U/238U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment 234U/238U activity ratios are close to 1.0. The 234U/238U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess 234U to the pore fluid by α-recoil injection of 234Th. The fraction of 238U decays that result in α-recoil injection of 234U to pore fluid is estimated to be 0.10 to 0.20 based on the 234U/238U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 4 × 10−7 to 2 × 10−6 yr−1. There is significant down-hole variability in pore water 234U/238U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 104 times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials.The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (Rd) of soils and deep-sea sediments can be approximately described by the expression Rd ≈ 0.1 Age−1 for ages spanning 1000 to 5 × 108 yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.  相似文献   

9.
The 230Th/234U/238U age dating of corals via alpha counting or mass spectrometry has significantly contributed to our understanding of sea level, radiocarbon calibration, rates of ocean and climate change, and timing of El Nino, among many applications. Age dating of corals by mass spectrometry is remarkably precise, but many samples exposed to freshwater yield inaccurate ages. The first indication of open-system 230Th/234U/238U ages is elevated 234U/238Uinitial values, very common in samples older than 100,000 yr. For samples younger than 100,000 yr that have 234U/238Uinitial values close to seawater, there is a need for age validation. Redundant 230Th/234U/238U and 231Pa/235U ages in a single fossil coral fragment are possible by Multi-Collector Magnetic Sector Inductively Coupled Plasma Mass Spectrometry (MC-MS-ICPMS) and standard anion exchange column chemistry, modified to permit the separation of uranium, thorium, and protactinium isotopes from a single solution. A high-efficiency nebulizer employed for sample introduction permits the determination of both 230Th/234U/238U and 231Pa/235U ages in fragments as small as 500 mg. We have obtained excellent agreement between 230Th/234U/238U and 231Pa/235U ages in Barbados corals (30 ka) and suggest that the methods described in this paper can be used to test the 230Th/234U/238U age accuracy.Separate fractions of U, Th, and Pa are measured by employing a multi-dynamic procedure, whereby 238U is measured on a Faraday cup simultaneously with all minor isotopes measured with a Daly ion counting detector. The multi-dynamic procedure also permits correcting for both the Daly to Faraday gain and for mass discrimination during sample analyses. The analytical precision of 230Th/234U/238U and 231Pa/235U dates is generally better than ±0.3% and ±1.5%, respectively (2 Relative Standard deviation [RSD]). Additional errors resulting from uncertainties in the decay constant for 231Pa and from undetermined sources currently limit the 231Pa/235U age uncertainty to about ±2.5%. U isotope data and 230Th/234U/238U ages agree with National Institute of Standards and Technology (NIST) reference materials and with measurements made by Thermal Ionization Mass Spectrometry (TIMS) in our laboratory.  相似文献   

10.
Authigenic carbonates and seep biota are archives of seepage history and record paleo-environmental conditions at seep sites. We obtained the timing of past methane release events at the northeastern slope of the South China Sea based on U/Th dating of seep carbonates and seep bivalve fragments from three sites located at 22°02′–22°09′N, 118°43′–118°52′E (water depths from 473 to 785 m). Also, we were able to reconstruct the paleo-bottom water temperatures by calculating the equilibrium temperature using the ages, the corresponding past δ18O of seawater (δ18Osw) and the δ18O of the selected samples formed in contact with bottom seawater with negligible deep fluid influence. A criterion consists of mineralogy, redox-sensitive trace elements and U/Th-isotope systematics is proposed to identify whether the samples were formed from pore water or have been influenced by deep fluid. Our results show that all methane release events occurred between 11.5 ± 0.2 and 144.5 ± 12.7 ka, when sea level was about 62–104 m lower than today. Enhanced methane release during low sea-level stands seems to be modulated by reduced hydrostatic pressure, increased incision of canyons and increased sediment loads. The calculated past bottom water temperature at one site (Site 3; water depth: 767–771 m) during low sea-level stands 11.5 and 65 ka ago ranges from 3.3 to 4.0 °C, i.e., 1.3 to 2.2 °C colder than at present. The reliability of δ18O of seep carbonates and bivalve shells as a proxy for bottom water temperatures is critically assessed in light of 18O-enriched fluids that might be emitted from gas hydrate and/or clay dehydration. Our approach provides for the first time an independent estimate of past bottom water temperatures of the upper continental slope of the South China Sea.  相似文献   

11.
Activity ratios of 234U/238U, 230Th/234U, and 230Th/232Th have been determined for calcite, gypsum and halite speleothems from caves of the Nullarbor Plain, mostly in the area N and NW of Mundrabilla Station, for the purpose of U-series dating. All calcite speleothems contain adequate amounts of uranium for dating, but some show an excess of 230Th. Stratigraphic relationships indicate that there were at least three phases of calcium carbonate deposition in the Nullarbor caves. The calcite samples, with one possible exception, have ages in excess of ca. 400000 yrs BP. This suggests that no significant amounts of calcium carbonate deposition have taken place during the last 400ka. At present, active deposition of speleothems is restricted almost entirely to gypsum and halite. The only gypsum speleothem dated was found to have a finite age of ca. 185 ka. Six dates on a small halite speleothem containing insect and arachnid remains indicate that it formed rapidly during Holocene time.  相似文献   

12.
Holocene sediments from the Gotland Deep basin in the Baltic Sea were investigated for their Fe isotopic composition in order to assess the impact of changes in redox conditions and a transition from freshwater to brackish water on the isotope signature of iron. The sediments display variations in δ56Fe (differences in the 56Fe/54Fe ratio relative to the IRMM-14 standard) from −0.27 ± 0.09‰ to +0.21 ± 0.08‰. Samples deposited in a mainly limnic environment with oxygenated bottom water have a mean δ56Fe of +0.08 ± 0.13‰, which is identical to the mean Fe isotopic composition of igneous rocks and oxic marine sediments. In contrast, sediments that formed in brackish water under periodically euxinic conditions display significantly lighter Fe isotope signatures with a mean δ56Fe of −0.14 ± 0.19‰. Negative correlations of the δ56Fe values with the Fe/Al ratio and S content of the samples suggest that the isotopically light Fe in the periodically euxinic samples is associated with reactive Fe enrichments and sulfides. This is supported by analyses of pyrite separates from this unit that have a mean Fe isotopic composition of −1.06 ± 0.20‰ for δ56Fe. The supply of additional Fe with a light Fe isotopic signature can be explained with the shelf to basin Fe shuttle model. According to the Fe shuttle model, oxides and benthic ferrous Fe that is derived from dissimilatory iron reduction from shelves is transported and accumulated in euxinic basins. The data furthermore suggest that the euxinic water has a negative dissolved δ56Fe value of about −1.4‰ to −0.9‰. If negative Fe isotopic signatures are characteristic for euxinic sediment formation, widespread euxinia in the past might have shifted the Fe isotopic composition of dissolved Fe in the ocean towards more positive δ56Fe values.  相似文献   

13.
Hydrogenetic ferromanganese crusts (Fe-Mn crusts) provide a secular record of the variations of seawater composition responding to changes in ocean circulation and erosion processes. In this respect, the acquisition of an absolute and reliable chronology in Fe-Mn crusts is a prerequisite. Here we combine four different and complementary chronometers (10Be, 230Thex, 230Thex/232Th, 234U/238U) in a Fe-Mn crust dredged at ∼2000 m depth in the east Atlantic to first establish a reliable chronology over the Quaternary period. Then, we use EDS chemical analysis to look for correlation between major element chemistry and climate changes. (230Thex), (230Thex/232Th), and Be data give very consistent growth rates. In particular, the good match between (230Thex) and (230Thex/232Th) data indicates that at the location of crust 121DK, 230Th and 232Th fluxes in the water column change simultaneously and suggests that the normalization of 230Thex to 232Th makes (230Thex/232Th) a better chronometer. Our best-fit model suggests that crust 121DK experienced changes in growth rates at ∼122 and 312 ka and a growth with a constant 230Th initial flux. This chronology returns an age of 680 ka for the uppermost 1.5 mm. The (234U/238U) depth profile, however, was clearly affected by diffusion of 234U in the porous crust and can therefore not be used to derive a reliable chronology. One part of the crust seems isolated from pore water diffusion and can be physically recognized as a zone of very small porosity. On the basis of the (230Thex/232Th) chronology, major element chemistry is shown to be linked to climate change. Mn/Fe variations compare well with those in a Fe-Mn crust from the Pacific, showing systematic maxima during glacial stages 2 and 4. High Mn/Fe are tentatively interpreted to reflect expansion of the oxygen minimum zone during glacial periods, resulting from higher bioproductivity. In addition we note that the surface (230Th/232Th) activity ratio of crust 121DK is entirely consistent with advection of deep water from the western toward the eastern Atlantic basin.  相似文献   

14.
A combined in situ SIMS and LA-(MC)-ICPMS study of U-Pb ages, trace elements, O and Lu-Hf isotopes was conducted for zircon from eclogite-facies metamorphic rocks in the Sulu orogen. The two microbeam techniques sampled various depths of zircon domains, revealing different element and isotope relationships between residual magmatic cores and new metamorphic rims and thus the geochemical architecture of metamorphic zircons which otherwise cannot be recognized by the single microbeam technique. This enables discrimination of metamorphic growth from different subtypes of metamorphic recrystallization. Magmatic cores with U-Pb ages of 769 ± 9 Ma have positive δ18O values of 0.1-10.1‰, high Th/U and 176Lu/177Hf ratios, high REE contents, and steep MREE-HREE patterns with negative Eu anomalies. They are interpreted as crystallizing from positive δ18O magmas during protolith emplacement. In contrast, newly grown domains have concordant U-Pb ages of 204 ± 4 to 252 ± 7 Ma and show negative δ18O values of −10.0‰ to −2.2‰, low Th/U and 176Lu/177Hf ratios, low REE contents, and flat HREE patterns with weak to no Eu anomalies. They are interpreted as growing from negative δ18O fluids that were produced by metamorphic dehydration of high-T glacial-hydrothermally altered rocks during continental subduction-zone metamorphism. Differences in δ18O between different domains within single grains vary from 0.8‰ to 12.5‰, suggesting different degrees of O isotope exchange between the positive δ18O magmatic core and the negative δ18O metamorphic fluid during the metamorphism. The magmatic zircons underwent three subtypes of metamorphic recrystallization, depending on their accessibility to negative δ18O fluids. The zircons recrystallized in solid-state maintained positive δ18O values, and REE and Lu-Hf isotopes of protolith zircon, but their U-Pb ages are lowered. The zircons recrystallized through dissolution exhibit negative δ18O values similar to the metamorphic growths, almost completely reset U-Pb ages, and partially reset REE systems. The zircons recrystallized through replacement show variably negative δ18O values, and partially reset REE, and U-Pb and Lu-Hf isotopic systems. Therefore, this study places robust constraints on the origin of metamorphic zircons in eclogite-facies rocks and provides a methodological framework for linking the different types of metamorphic zircons to petrological processes during continental collision.  相似文献   

15.
U-series disequilibria measured in waters and rocks from a chalk aquifer in France have been used as an analog for long-term radionuclide migration. Drill core samples from a range of depths in the vadose zone and in the saturated zone, as well as groundwater samples were analyzed for 238U, 234U, 232Th and 230Th to determine transport mechanisms at the water/rock interface and to quantify parameters controlling the migration of radionuclides. Isotope measurements in rocks were done by TIMS, whereas (234U/238U) and (230Th/232Th) activity ratios in water samples were measured by multi-collector-ICP-MS. Both depletion and enrichment in 234U relative to 238U were observed in carbonate rock samples resulting from chemical weathering in the unsaturated zone and calcite precipitation in the zone of water-table oscillation, respectively. The correlation between (230Th/232Th) activity ratios and 87Sr/86Sr ratios found in the chalk samples indicates that thorium is mainly contained in a minor silicate phase whose abundance is variable in chalk samples. Water samples are all characterized by (234U/238U) > 1 resulting from α-recoil effect of 234Th. Groundwaters are characterized by a more radiogenic signature in 87Sr/86Sr than the rocks. Moreover, (230Th/232Th) activity ratios in the waters are lower than in the rocks, and increase with distance from the water divide, which suggests that Th transport is controlled by colloids formed during water infiltration in the soil. A 1-D transport model has been developed in order to constrain the U-series nuclide transport considering a transient behavior of radionuclides in the aquifer and a time-dependent composition for the solid phase. This model permits a prediction of the time scale of equilibration of the system, and an estimation of parameters such as weathering rate, distribution coefficients and α-recoil fractions. Retardation factors of 10-35 and from 1 × 104 to 2 × 105 were predicted for U and Th, respectively, and can be used to predict the migration of radionuclides released as contaminants in the environment. At the scale of our watershed (∼32 km2), a characteristic migration time from recharge to riverine discharge of 200-600 yr for U and 0.2-3.7 Myr for Th was obtained.  相似文献   

16.
Extreme U and Pb isotope variations produced by disequilibrium in decay chains of 238U and 232Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my−1) contain excess 206Pb and 208Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable 206Pb/238U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect 207Pb/235U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages.Opal and calcite from outer (younger) portions of coatings have 230Th/U ages from 94.6 ± 3.7 to 361.3 ± 9.8 ka and initial 234U/238U activity ratios (AR) from 4.351 ± 0.070 to 7.02 ± 0.12, which indicate 234U enrichment from percolating water. Present-day 234U/238U AR is ∼1 in opal/chalcedony from older portions of the coatings. The 207Pb/235U ages of opal/chalcedony samples range from 0.1329 ± 0.0080 to 9.10 ± 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my−1, in good agreement with previous results. Measured 234U/238U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ± 0.006 to 2.091 ± 0.006 and are >1 in most samples. The range of 87Sr/86Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool.In the U-poor calcite samples, measured 206Pb/207Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both 206Pb and 207Pb derived from Rn diffusion and from direct α-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains 206Pb and 208Pb excesses, but no appreciable 207Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect 206Pb-238U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.  相似文献   

17.
Activity profiles of excess 234Th, excess 210Pb, 232Th, 230Th, 234U and 238U, and 228/232Th ratios determined in eight box cores of sediment from six sites in central Puget Sound provide new insights into the dynamic nature of solid phase mixing in surface sediments, the exchange of 228Ra and other soluble species across the sediment-water interface, and the cycling of U, Th and 210Pb in this coastal zone.Comparison of excess 234Th inventories in sediments with its production rate in the overlying water column indicates a mean residence time of at most 14 days for particles in the central Puget Sound water column.Surface sediment horizons with excess 234Th have no excess 228Th which might be used to ascertain sediment accumulation rates over the past decade. Instead, deficiencies of 228Th due to loss of soluble 228Ra from pore water to the overlying water persist to 20–30 cm, revealing that exchange of soluble chemicals between pore and overlying waters reaches these depths in the extensively bioturbated sediments of Puget Sound.Solid phase U isotope concentrations tend to increase by up to a factor of two with depth in sediments, as a result of dissolved U being biologically pumped down into sediments where it is partially removed when conditions become mildly reducing. 232Th and 230Th activities and 230/232Th ratios are constant with depth in sediments, indicating constant detrital phase compositions and essentially no authigenic 230Th. Steady state 210Pb depositional activities in and fluxes to Puget Sound sediments average only about onehalf those for sediments of the open Washington coast north of the Columbia River mouth, primarily because of a much lower supply of dissolved 210Pb in sea waters adverting into Puget Sound.Excess 234Th profiles in sediments reveal much more detail about the depth dependency, dynamic nature and recent history of solid phase mixing processes than excess 210Pb profiles. At least six of eight 234Th profiles show that mixing within the 210Pb-defined surface mixed layer is depth dependent. In three profiles, 234Th-derived mixing rates are fastest several centimeters below the sediment-water interface, indicating greater macro-benthic activity at these depths. Depth dependent mixing coefficients derived from the best fit of a four layer, advection-diffusion-decay model to the 234Th data are consistent with 210Pb profiles determined for the same sediments, strongly suggesting that 234Th and 210Pb are mixed equivalently and in a multilayered manner.  相似文献   

18.
U-series activity ratios, Sr-Nd-Pb isotopic ratios and major and trace element compositions have been determined on young basalts (<10 ka) and trachytes from the volcano Emuruangogolak in the Kenya Rift Valley. The basalts are mildly alkaline and are associated with small volumes of hawaiite. The mafic rocks are characterised by high (230Th/232Th) (≥1.06) with low (238U/230Th) ratios (≤0.72). They have variable incompatible trace element ratios (e.g. Zr/Nb, Ba/Zr), indicating that they represent a number of magmatic lineages. The trachytes, which comprise both comenditic and pantelleritic varieties, have significantly lower (230Th/232Th) ratios than the basalts, with clear differences between pantelleritic and comenditic types. The (238U/230Th) ratios in the pantellerites range from less, to greater, than 1. The variations in composition and isotopic diversity must represent different sources for the trachytes. Internal isochrons for the trachytes give U-Th ages of 14 to 40 ka, similar to single crystal laser fusion 40Ar/39Ar ages from sanidine phenocrysts (16–38 ka) for the same rocks. Post-crystallisation residence times of the trachytes were very short, implying relatively rapid movement of trachyte from magma chamber to the surface. Variations in the initial (230Th/232Th)0 ratios (0.69–1.14) of both basalts and trachytes indicate that Emuruangogolak has erupted a large range of isotopically diverse magmas over a very short period of time (38 ka), from conduits closely spaced around the summit of the volcano. Received: 29 May 1996 / Accepted: 24 November 1997  相似文献   

19.
In order to determine the geochemical evolution of a freshwater limestone cave system located in central Switzerland (Hell Grottoes at Baar/Zug,) young postglacial tufaceous limestone and travertine precipitates were investigated using the 230Th/234U ingrowth system. Additional analyses of further radionuclides within the 238U decay chain, i.e. 226Ra and 210Pb, showed that the Th/U chronometer started with insignificant inherited 230Th over the entire formation period of the travertine setting (i.e. 230Th(0)=0). A contribution from detrital impurities with 230Th/234U in secular equilibrium could be precisely subtracted by applying isochron dating of cogenetic phases and recently formed travertine. The resulting precise 230Th/234U formation ages were found to be consistent with the geological stratigraphy and were furthermore used to demonstrate the applicability of the next geologically important chronometer in the 238U-decay series, based on decay of excess 226Ra normalized to the initial, i.e.226Raex/226Ra(0). This system is suitable for dating phases younger than 7000 yr when the correction of a detritus component increasingly limits the precision of the 230Th/234U chronometer. Analytical solutions of the coupled 234U/230Th/226Ra radionuclide system predicted that the 226Raex/226Ra(0) chronometer is independent of the actual 230Th activity build up from decay of 234U, if the systems starts with zero inherited 230Th(0). The data set confirmed this hypothesis and showed furthermore that the initially incorporated 226Ra excess must have remained almost uniform in all limestone over a period of at least 7000 yr, i.e. 4–5 half-lives of 226Ra. This is concluded because (i) the 226Raex/226Ra(0) ages agreed well with those derived from 230Th/234U, (ii) all data plot within uncertainty on the 226Raex/226Ra(0) decay curve and (iii) the atomic Ba/Ca ratio was found to be constant in the travertine material independent of the sample ages. Provided that such boundary conditions hold, 226Raex/226Ra(0) should be applicable to materials which are suitable for 230Th/234U dating in sedimentology and oceanography, i.e. travertine, corals, phosphorites, etc., and should strongly support 230Th/234U for samples that have been formed a few thousand years ago.  相似文献   

20.
An 18 million year record of the Ca isotopic composition (δ44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. δ44/42Ca in this record averages +0.37 ± 0.05 (1σ SD) and ranges from +0.21‰ to +0.52‰. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25‰ lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their δ44/42Ca (i.e., by 0.06 ± 0.06‰ (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in δ44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (δ44/42Caw) and for isotope fractionation associated with the production of carbonate sediments (Δsed) results in unrealistically large variations in the total mass of Ca2+ in the oceans over the Neogene. Alternatively, variations of ±0.05‰ in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in δ44/42Caw of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in Δsed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in δ44/42Caw and Δsed have been established, modeling the Ca2+ content of seawater from Ca isotope curves should be approached cautiously.  相似文献   

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