Distribution of 238U, 232Th and 40K in plutonic rocks of Greece

One hundred and twenty one samples from every major plutonic body (mainly granitic) of Greece have been analyzed by γ-ray spectrometry to determine the specific activities of ²³⁸U, ²³²Th and ⁴⁰K (Bq/kg). The range of the activity concentrations of these radionuclides was 2.3–266.4, 1.8–375.5 and 55.0–1632.0 Bq/kg and their average values were 79.2, 85.3 and 881.4 Bq/kg respectively. Any possible connection between the specific activities of ²³⁸U, ²³²Th and ⁴⁰K and some characteristics of the studied samples (age, rock-type, colour, grain-size, occurrence and chemical composition) is investigated. Samples of particular colour, rock-type, occurrence and chemical composition have been identified for their distinctive levels of natural radioactivity, while age and grain-size do not affect the concentrations of ²³⁸U, ²³²Th and ⁴⁰K. The range of the Th/U ratio was 0.7–12.69. This great variation in the Th/U ratios, especially when it is found among the samples of the same pluton, is also discussed and explained by alteration and tectonic–metamorphic processes.     

238U/206Pb-235U/207Pb-232Th/208Pb zircon geochronology in alpine and non-alpine environment

Based on regular arrays in a U-Pb diagram of data points of zircons from polymetamorphic rocks of the Alps quantitative models are developed that include several episodic lead losses, continuous lead losses during discrete periods and combinations of both.The data from the Alps can be explained by assuming an initial age of the zircons of 2000 and/or 2500–2600 m.y. and three episodic lead losses 520–580 m.y., 300 m.y. and 30 m.y. ago with regionally varying intensities of the events as can be seen from the efficiency parameters which define the shape of the discordia. On the other hand, zircon data from North American basement rocks satisfy a model assuming a discrete interval of continuous lead loss that starts with the time of uplift of the rocks.The Th-U-Pb diagrams are valuable for recognising whether the history of the zircons and their host rock is a complex one or not which is not always noticeable in a U-Pb diagram.     

TIMS测定铀矿石样品中^234U/^238U、^230Th/^232Th、^228Ra/^226Ra的方法研究

研究了TIMS测定铀矿石样品中234U/238U、230Th/232Th、228Ra/226Ra的方法。建立了铀矿石密闭混酸一次溶样的方法和采用阴离子、阳离子和Sr特效树脂逐级离子交换分离纯化U、Th和Ra的流程,满足了TIMS测量要求。测定结果表明：100～1000 ng的天然铀中234U/238U,其测量精密度从静态多接收的2.34%提高到动态多接收的0.47%;对230Th与232Th丰度接近、质量为1μg左右的钍,采用三带点样技术和法拉第多接收技术测定230Th/232Th,其内精度平均值为0.0048%,外精度为0.028%;采用单带加钽发射剂,ETP跳峰测定50～100 fg镭-228稀释剂中的228Ra/226Ra,其内精度小于0.10%,外精度小于0.20%。比较TIMS和HR-ICP-MS、α能谱法测定234U/238U、230Th/232Th、228Ra/226Ra结果,三者结果相吻合。TIMS测量法样品用量少、快速、准确、精密度高,是U、Th、Ra同位素比值测定方法的又一补充。     

234U238U and 230Th234U activity ratios in mineral phases of a lateritic weathered zone

A selective phase extraction procedure was developed for the identification of the significant phases of a typical deep soil profile sampled in the vicinity of the Ranger No. 1 uranium ore body, Alligator Rivers region, N.T., Australia. The significant phases were identified as amorphous iron oxide, crystalline iron oxide and a clay/quartz resistate. The distribution of ²³⁸U, ²³⁴U, ²³⁰Th and ²²⁶Ra between the phases was measured. The results indicated that the amorphous iron oxide phase is in adsorption/desorption equilibrium with the ground water. The crystalline iron oxide phase contains a chemical control, the kinetics of which are commensurate with or less than the half-life of ²³⁰Th (7.52 × 10⁴ y). The clay/quartz resistate is enriched in ²³⁸U descendants in such a way that they are not readily accessible to the ground water.     

Analysis of the atmospheric 14C record spanning the past 50,000 years derived from high-precision 230Th/234U/238U, 231Pa/235U and 14C dates on fossil corals

Changes in the geomagnetic field intensity, solar variability, and the internal changes of the carbon cycle are believed to be the three controlling factors of past atmospheric radiocarbon (¹⁴C) concentrations (denoted as Δ¹⁴C). Of these three, it is believed that the field intensity is the dominant factor. We analyze an atmospheric Δ¹⁴C record spanning the past 50,000 years based on previously-published ²³⁰Th/²³⁴U/²³⁸U and ¹⁴C dates of fossil corals from Kiritimati, Barbados, Araki and Santo Islands, and identify the role of the Laschamp geomagnetic field excursion on the long term trend of the Δ¹⁴C record. There is a general consistency between the coral Δ¹⁴C record and the Δ¹⁴C output from carbon cycle models based on the global ¹⁴C production estimates. High-precision, high-accuracy ²³⁰Th/²³⁴U/²³⁸U dates and redundant ²³¹Pa/²³⁵U dates anchor the timing of this Δ¹⁴C record. We propose that a significant fraction of the long-term Δ¹⁴C trend may be due to inaccuracies in the generally accepted ¹⁴C decay constant. The uncertainty in estimating the shape of ¹⁴C beta spectrum below 20 keV leads to one of the greatest errors in decay constant estimates. Once the ¹⁴C half-life is validated via redundant techniques, Δ¹⁴C records will provide a better opportunity to examine the roles of carbon cycle and ¹⁴C production influences.     

Extreme fractionation of 234U238U and 230Th234U in spring waters,sediments, and fossils at the Pomme de Terre Valley,southwestern Missouri

Isotopic fractionation as great as 1600% exists between ²³⁴U and ²³⁸U in spring waters, sediments, and fossils in the Pomme de Terre Valley, southwestern Missouri. The activity ratios of ${}^{234}\text{U}{}^{238}\text{U}$ in five springs range from 7.2 to 16 in water which has been discharged for at least the past 30,000 years. The anomalies in ${}^{234}\text{U}{}^{238}\text{U}$ ratio in deep water have potential usefulness in hydrologic investigations in southern Missouri. Clayey units overlying the spring bog sediments of Trolinger Spring are enriched in ²³⁰Th relative to their parent ²³⁴U by as much as 720%. The results indicate that both preferential displacement via alpha recoil ejection and the preferential emplacement via recoiling and physical entrapment are significant processes that are occurring in the geologic environment.     

234Th238U radioactive disequilibrium in the surface layer of the ocean

²³⁴Th produced from ²³⁸U within sea water was found to be in radioactive disequilibrium with respect to its progenitor nuclide ²³⁸U in the surface layer of the ocean. The median value for ${}^{234}\text{Th}{}^{238}\text{U}$ activity ratio is 0.80 in the upper 200 m layer. A box-model calculation gives a removal residence time of thorium of about 0.38 yr. This suggests that ²³⁴Th is scavenged from the surface layer by the uptake of thorium by biota.     

Th/U/U and Pa/U ages from a single fossil coral fragment by multi-collector magnetic-sector inductively coupled plasma mass spectrometry

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/²³⁸U_initial values, very common in samples older than 100,000 yr. For samples younger than 100,000 yr that have ²³⁴U/²³⁸U_initial 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.     

In situ sulfur isotope analysis by laser ablation MC-ICPMS

A new method for in situ S isotopic analysis was tested using a laser ablation system together with a multi-collector (MC)-ICPMS. The method was tested for the analysis of pyrite, pyrrhotite, chalcopyrite and pentlandite using a large pyrite crystal as an in-house standard. Repeated measurements of Py, Pn, Po and Cpy provide an average internal precision of less than 0.1‰ (2σ). The method was also applied to a pyrite-bearing orogenic Au deposit to display the ability of the method to resolve minor variations in δ³⁴S across growth zoning in pyrite.     

平面型高纯锗低能γ谱仪测定铀矿样中^235U,^238U,^226Ra及^232Th含量

本文对选用低能γ射线测定铀矿中的~(235)U、~(238)U、~(226)Ra、~(232)Th含量进行了讨论,提出了一种对样品进行自吸收校正的简单准确方法,对铀矿样中的~(235)U、~(238)U、或~(235)U/~(238)U比值测定获得了较高的分析精度和准确度。     

U and Th concentrations and isotope ratios in modern carbonates and waters from the Bahamas

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.     

ESR isochron dating analyses at Bau de l'Aubesier,Provence, France: Clues to U uptake in fossil teeth

At Bau de l'Aubesier, Provence, Mousterian artifacts and human teeth occur in inhomogeneous (“lumpy”) sedimentary deposits that include bone and tooth fragments and extensive burnt horizons. Electron spin resonance (ESR) isochron analyses of mammal teeth, which use multiple subsamples with different U concentrations, can measure the external dose rate experienced by the tooth regardless of reworking and sedimentary dose rate changes. Isochron analyses do depend on the U uptake model assumed, but can also identify teeth that have experienced secondary U uptake or leaching. Using 11 teeth from six archaeological layers, the isochrons demonstrate that at least three teeth have experienced secondary uptake. For eight teeth, the U uptake has apparently not followed strictly early (EU), linear (LU), or recent uptake (RU), but more closely approximates LU‐RU. Comparing volumetrically averaged sedimentary geochemistry with thermoluminescent dosimetry suggests that fossil tissues in the sediment have also experienced LU‐RU uptake. LU‐RU uptake can explain standard ESR ages that underestimate the true fossil age. © 2001 John Wiley & Sons, Inc.     

Timing and intensity of groundwater movement during Egyptian Sahara pluvial periods by U-series analysis of secondary U in ores and carbonates

Wet climatic episodes are known to have prevailed in the Egyptian Sahara several times during the late Quaternary, most recently during the Holocene 8000 yr ago. Earlier wet episodes have been recognized as having occurred during the past 300,000 yr and have been dated by U-series methods in speleothems and in lake travertines. We show here that the times of enhanced groundwater movement can also be determined by ²³⁰Th/²³⁴U dating of secondary U in ores of uranium, iron, and phosphate. We also present evidence that such acceleration of groundwater movements is indicated by relatively low ²³⁴U/²³⁸U activity ratios in the secondary uranium. Our new data show that pluvial periods in Egypt occurred during marine oxygen isotope stages 4, 5, 6, and 7 and therefore are consistent with the view that the wet episodes are the results of migration of the tropical monsoonal belt driven primarily by the 23,000-yr precession cycle of the Milankovich curve, modulated by the 100,000-yr eccentricity cycle.     

High resolution analysis of uranium and thorium concentration as well as U-series isotope distributions in a Neanderthal tooth from Payre (Ardèche, France) using laser ablation ICP-MS

We have mapped U (²³⁸U) and Th (²³²Th) elemental concentrations as well as U-series isotope distributions in a Neanderthal tooth from the Middle Palaeolithic site of Payre using laser ablation ICP-MS. The U-concentrations in an enamel section varied between 1 and 1500 ppb. The U-concentration maps show that U-migration through the external enamel surface is minute, the bulk of the uranium having migrated internally via the dentine into the enamel. The uranium migration and uptake is critically dependent on the mineralogical structure of the enamel. Increased U-concentrations are observed along lineaments, some of which are associated with cracks, and others may be related to intra-prismatic zones or structural weaknesses reaching from the dentine into the enamel. The uranium concentrations in the dentine vary between about 25,000 and 45,000 ppb. Our systematic mapping of U-concentration and U-series isotopes provides insight into the time domain of U-accumulation. Most of the uranium was accumulated in an early stage of burial, with some much later overprints. None of the uranium concentration and U-series profiles across the root of the tooth complied with a single stage diffusion-adsorption (D-A) model that is used for quality control in U-series dating of bones and teeth. Nevertheless, in the domains that yielded the oldest apparent U-series age estimates, U-leaching could be excluded. This means that the oldest apparent U-series ages of around 200 ka represent a minimum age for this Neanderthal specimen. This is in good agreement with independent age assessments (200-230 ka) for the archaeological layer, in which it was found.The Th elemental concentrations in the dental tissues were generally low (between about 1 and 20 ppb), and show little relationship with the nature of the tissue.     

U and Th zonation in apatite observed by laser ablation ICPMS, and implications for the (U-Th)/He system

A laser-ablation inductively-coupled plasma mass spectrometry technique was developed to measure U, Th, and Ce zonation in polished sections of apatite for assessing the consequences of parent zonation for (U-Th)/He thermochronometry. The technique produces concentration maps with an averaging length-scale of ∼20 μm, comparable to the α-stopping distance, and a precision of ∼5% down to few ppm concentration levels. A model was developed to transform the measured concentration distribution into a simplified representation for use in spherical-geometry He production-diffusion models. To illustrate these methods, 30 sections of apatite from a single granite (GC863) were mapped. Every analyzed apatite from GC863 is zoned, with most grains having variable thickness rims and terminations that are enriched in U and Th by about a factor of three over the grain cores.Parent zonation has three independent effects on (U-Th)/He He ages: it influences the α ejection correction, the ⁴He concentration profile which governs diffusive loss, and, via radiation damage trap accumulation, spatial variability of diffusivity within the crystal. If the observed zonation is typical of the apatite population in GC863, use of the standard homogenous α ejection correction would cause He ages to be on average 3% too young, and with a large amount of grain-to-grain variability (9% too young in the most rim-enriched case to 6% too old in a core-enriched case). Independent of the ejection correction, the concentration profile modifies the effective closure temperature of the apatites by placing more (or less) ⁴He near the grain edge. The parent zonation in GC863 apatites causes closure temperatures to range from four degrees lower (rim-enriched case) to two degrees higher (core-enriched case) than applies in the homogenous case. Alpha ejection and concentration profile effects on He age are additive and of the same sense. In the case of typical grains in GC863 cooled between 1 and 10 °C/Ma, the two effects are roughly equal in magnitude. The effects of intracrystalline variations in radiation damage trap accumulation become apparent at slow cooling rates (1 °C/Ma). For example, in rim-enriched GC863 grains cooled at 1 °C/Ma, preferential accumulation of radiation damage traps near the grain rim almost compensates for the higher loss rate expected of ⁴He also located preferentially near the rim. Under some circumstances strong rim-enrichment may actually increase the effective closure temperature of an apatite. Zonation at the level observed in GC863 modifies the ⁴He/³He spectra substantially from that expected from a uniform distribution. Measured ⁴He/³He spectra are strikingly similar to predictions based on the mapped eU distributions of the very same crystals, supporting the overall validity of the analytical and interpretive approach presented here.The magnitude and style of U, Th zonation documented in GC863 is one possible source of frequently observed over-dispersion of apatite (U-Th)/He ages as well as anomalous ⁴He/³He spectra.     

Crystallization history of rhyolites at Long Valley, California, inferred from combined U-series and Rb-Sr isotope systematics

In this study, we present ⁸⁷Rb/⁸⁶Sr and ²³⁰Th/²³⁸U isotope analyses of glasses and phenocrysts from postcaldera rhyolites erupted between 150 to 100 ka from the Long Valley magmatic system. Both isotope systems indicate complex magma evolution with preeruptive mineral crystallization and magma fractionation, followed by extended storage in a silicic magma reservoir. Glass analyses yield a Rb-Sr isochron of 257 ± 39 ka, which can be explained by a feldspar-fractionation event ∼150 ky before eruption. Individual feldspar-glass pairs confirm this age result. A mineral ²³⁰Th-²³⁸U isochron in a low-silica rhyolite from the Deer Mountain Dome defines an age of 236 ± 1 ka, but the glass and whole rock do not lie on the isochron. U-Th fractionation of the rocks is controlled by the accessory minerals zircon and probably allanite, which crystallized at 250 ± 3 ka and 187 ± 9 ka, respectively. All major mineral phases contain accessory mineral phases; therefore, the mineral isochron represents a mixture of zircon and allanite populations. A precision of ±1 ka for the mixing array implies that the minor phases must have crystallized within this timescale. Longer periods of crystal growth would cause the mixing array to be less well defined. U-series data from other low- and high-silica rhyolites indicate younger accessory mineral crystallization events at ∼200 and 140 ka, probably related to the thermal evolution of the magma reservoir. These crystallization events are, however, only documented by the accessory minerals and had no further influence on bulk magma compositions. We interpret the indistinguishable age results from both isotope systems (∼250 ka) to record the fractionation of small magma batches by filter pressing from a much larger underlying magma volume, followed by physical isolation and extended storage at the top of the magma reservoir for up to 150 ky.     

U—Series Dating of Fossil Bones：Results from Chinese Sites and Discussions on Its Reliability

Calculations,according to some open-system models,point out that while a statistically significant discrepancy between the results of two U-series methods,^230Th/^234U and ^227Th/^220Th(or ^231Pa/^235U),attests a relatively recent and important uranium migration,concordant dates cannot guarantee closes-system behavior of sample.The results of 20 fossil bones from 10 Chinese sites,19 of which are determined by two U-series methods,are given,Judging from independent age controls,8 out of the 11 concordant age sets are unacceptable,The results in this paper suggest that uranium may cycle into or out of fossil bones,such geochemical events may take place at any time and no known preserving condition may securely protect them from being affected.So for the sitew we have studied,the U-series dating of fossil bones is of limited reliability.     

On the limits of using combined U-series/ESR method to date fossil teeth from two Early Pleistocene archaeological sites of the Orce area (Guadix-Baza basin,Spain)

The combined U-series/electron spin resonance (ESR) dating method was applied to nine teeth from two Early Pleistocene archaeological sites located in the Orce area (Guadix-Baza Basin, Southern Spain): Fuente Nueva-3 (FN-3) and Barranco León (BL). The combination of biostratigraphy and magnetostratigraphy places both sites between the Olduvai and Jaramillo subchrons (1.78–1.07 Ma).Our results highlight the difficulty of dating such old sites and point out the limits of the combined U-series/ESR dating method based on the US model. We identified several sources of uncertainties that may lead to inaccurate age estimates. Seven samples could not be dated because the dental tissues had (²³⁰Th/²³⁴U) activity ratios higher than equilibrium, indicating that uranium had probably leached from these tissues. It was however possible to calculate numerical estimates for two of the teeth, both from FN-3. One yielded a Middle Pleistocene age that seems to be strongly underestimated; the other provided an age of 1.19 ± 0.21 Ma, in agreement with data obtained from independent methods. The latter result gives encouragement that there are samples that can be used for routine dating of old sites.     

Scavenging and particle residence times determined from 234Th/238U disequilibria in the coastal waters of Mecklenburg Bay

Activities of the naturally occurring radionuclide ²³⁴Th were determined in water samples of Mecklenburg Bay (SW Baltic Sea) using a new Th-specific diatomite adsorption technique followed by liquid scintillation spectrometry. Activities of “dissolved” (operationally defined as Th in the centrifugate) and particulate ²³⁴Th varied in the range of 1.4–6.9 and 0.9–9.3 mBq l⁻¹, respectively. A significant correlation between K_d and SPM concentration was found. From this particle-concentration effect, the “colloidal pumping” model predicts that 98% of the “dissolved” Th is associated with colloids rather than being truly dissolved. Relative to calculated activities of the parent nuclide ²³⁸U in the Bay, the ²³⁴Th data yielded mean ²³⁴Th scavenging residence times in the range of 1.2–9.7 days. Particulate ²³⁴Th activities are inversely correlated to SPM concentrations. Particle residence times ranged from a few days in winter up to 20 days in spring characterized by less intense bottom currents. The hydrodynamic regime is the master variable controlling scavenging of Th and other similarly particle-reactive elements in Mecklenburg Bay.