高分辨电感耦合等离子体质谱法测定铀矿石样品中234U/238U、230Th/232Th和228Ra/226Ra同位素比值 

采用氢氟酸-硝酸-盐酸混合酸密闭消解含铀矿石样品,用阴离子交换树脂、阳离子交换树脂和锶特效树脂逐级分离富集铀、钍和镭。使用高分辨电感耦合等离子体质谱(HR-ICPMS)测定分离纯化液中234U/238U2、30Th/232Th和228Ra/226Ra同位素。比值的测量精密度取决于比值的大小和对应核素浓度的大小。对质量浓度为10 ng/mL天然铀测量液,234U/238U的测量精密度优于1.2%;对230Th质量浓度为0.6ng/mL且230Th和232Th质量浓度接近的测量液,230Th/232Th的测量精密度为1.2%;对228Ra质量浓度为0.48 pg/mL且228Ra和226Ra质量浓度接近的测量液,228Ra/226Ra的测量精密度为4.0%。     

我国西北地区盐湖中的铀234U/238U比值示踪研究

内蒙古二连盆地、鄂尔多斯盆地典型含铀碳酸型盐湖水、岩两相234U/238U综合分析表明,碳酸型盐湖铀来源于大气降水和潜水对盐湖盆地周围中生代到现代富铀沉积物的溶滤、浸出,具有快速、近源物质来源特点。盐湖卤水和对应沉积物234U/238U值一般为0.8～1.2,湖卤水和潜卤水（晶间卤水）-岩两相中的铀处于沉积平衡状态。早白垩世～上新世含膏盐地层对比研究证实了富铀岩层234U/238U值随铀含量增大而减小,并趋近于1。室内盐湖水蒸发模拟实验发现残余卤水、沉积物234U/238U具有随蒸发程度增大逐渐减小的变化特征。盐湖现代沉积物物相研究发现铀主要以碳酸铀酰和吸附形式赋存在富含有机物和碎屑成分的含盐粘土沉积中,铀在盐类晶体中含量极少,仅存在于封闭水和结晶水中。卤水和沉积物ARu值是盐湖铀源及铀含量水平的指示标志之一。     

234Th/238U不平衡法在真光层颗粒动力学研究中的应用

真光层是海洋浮游生物活动最为活跃的区域,其间发生的颗粒动力学过程及其机制对于海洋碳的生物地球化学循环有着重要影响,利用放射性核素示踪海洋真光层颗粒动力学过程成为近年来海洋科学的前沿课题。介绍了该领域＾２３４Ｔｈ－＾２３８Ｕ不平衡法的原理、发展历程及其在ＰＯＣ输出通量的估算、沉积物捕集器捕集效率的校正、真光层层化结构的揭示、颗粒活性元素固／液界面分配机制的研究、海洋胶体性质的研究及近岸海域悬浮颗粒活     

洞穴碳酸盐230Th-234U-238U测年初始钍校正的等时线研究

初始钍的校正是不纯沉积碳酸盐230Th 234U 238U测年的一个重要方面，洞穴石笋初始Th校正通常采用230Th/232Th的原子比值为（4.4±2.2）×10-6。多年来4种不同的等时线方法应用到不纯碳酸盐测年初始Th的校正中，其中全样品的等时线方法是目前公认的较为完善的一种方法。通过测定云南同一石笋2个不同层位的9个样品的U、Th同位素组成,并进行等时线分析，结果表明2层样品初始钍230Th/232Th原子比值分别为（3.5±2.8）×10-6和（10.6±2.2）×10-6，这说明即使在同一地区，由于其混入Th来源的复杂性，230Th/232Th初始比值在同一样品不同层位仍可能有较大的差异，因此不能够完全采用单一层位等时线获得的初始值对整个样品进行校正。考虑到在实验测量过程中，232Th含量的过高对于230Th的准确测定也有很大的影响，应尽量选择纯净石笋样品进行测年研究，在样品的选择和前处理过程中就减少初始钍的影响，这对获得高精度的测年结果有着重要的意义。     

石笋初始234 U/238 U值的冰量周期特征及其环境意义 ——以湖北三宝洞为例

石笋氧同位素记录具有明显的2万年周期,其他记录中广泛存在的10万年周期是否在石笋中有所表现目前还鲜有报道。通过对湖北三宝洞20支石笋的铀同位素数据的分析研究发现,石笋初始234U/238U值在序列连续性较好的640.3~299.6 ka B.P.时间段有强烈的10万年周期特征。在间冰期和冰期时,初始234U/238U值分别呈增大和减小状态。初始234U/238U值的10万年周期与全球冰量、黄土磁化率、黄土平均粒度和大气CO₂变化有良好的对应关系。这些对应关系表明全球冰量、大气CO₂对喀斯特区地球化学元素富集和迁移作用有重要影响。石笋氧同位素的显著岁差周期独立于石笋微量元素、高纬冰量和全球温室气体变化,暗示了太阳辐射变化对中低纬水汽环流的直接影响。石笋初始234U/238U与氧同位素、太阳辐射在冰消期时的对应变化支持北半球太阳辐射能量变化对冰期-间冰期旋回的调控作用。     

中子活化分析法测定地质样品中铀的^235U／^238U比值

对于^235U/^238U比值的测定，不但对于核燃料工业是必不可少的，而且在铀矿地质科学和基础科学研究中也有着重要的意义。同位素比值通常采用质谱法测定；对于铀也可通过天然放射性测量，测定^235U/^238U比值，但所需的样品量大(精确测定需0．5g左右的     

不采用同位素示踪剂测定地质样品中^234U,^238U,^230Th和^232Th比活…

本提出了不采用同位素示踪剂测定铀，钍同位素比活度的方法。用标准方法准确的测定地质样品中的铀，钍含量及＾２３４Ｕ／＾２３８Ｕ，＾２３０Ｔｈ／＾２３２Ｔｈ的活度比值，再应用铀，钍系的衰变特性，推导出计算样品中＾２３４Ｕ，＾２３８Ｕ，＾２３０Ｔｈ和＾２３２Ｔｈ经活度的方法，本方法计算所得之结果与＾２３２Ｕ示踪法对比。均在１σ范围内，符合很好。     

洞穴石笋初始234U/238U值变化的古气候记录意义

通过对我国西南地区3个洞穴9根大型石笋272个初始234U/238U数据的分析研究,发现石笋初始234U/238U值长尺度变化与海洋沉积SPECMAP曲线δ18O记录有一定的正相关关系,与北纬25°夏季太阳辐射能量变化曲线呈一定的负相关关系,石笋初始234U/238U值的变化在冰期时波动强烈,而在间冰期波动相对平缓,在间冰期和冰期(间冰阶和冰阶)转化阶段该值呈跳跃状态变化。末次冰期及全新世阶段石笋初始234U/238U变化记录了该时段内的BA暖期和YD突变冷事件;全新世8200 a BP、7200 a BP、5200 a BP、4200 a BP、2800 a BP、1400 a BP 发生的几次较强冷事件在石笋初始234U/238U值都有相应记录,并且和长尺度的变化规律一致,冷事件发生时石笋初始234U/238U值偏重,暖期偏轻。封闭系统形成的洞穴石笋初始234U/238U变化类似于同地区洞穴石笋的δ18O对气候变化的记录特征,在我国西南地区两者与夏季风变化的强弱呈现一种负相关的关系,洞穴石笋初始234U/238U值可以作为一个有用的古气候替代指标来研究古降水的变化。     

我国西北地区盐湖中234U/238U比值与铀关系研究——以内蒙古地区碳酸盐型盐湖为例

内蒙古二连盆地、鄂尔多斯盆地典型含铀碳酸型盐湖水、岩两相2344U/23898U综合分析表明,该类盐湖铀来源于降水和潜水对盐湖盆地周围中生代以来富铀沉积物的溶滤、浸出,具有快速、近源物质来源特点.盐湖卤水和对应沉积物234 U/238U比值一般为0.8～1.2,盐湖卤水和潜卤水(晶间卤水)岩两相中的铀处于沉积平衡状态.含铀盐湖水、沉积物的234 U/238U比值随其铀含量增大而减小,并趋近于1,富铀盐湖水及沉积物234U/238U比值介于0.9～1.5之间.室内盐湖水蒸发模拟实验发现,残余卤水、沉积物234U/238U、铀总量具有随蒸发程度增大逐渐减小的变化特征.铀主要以碳酸铀酰络合物和吸附形式赋存在富含有机物和碎屑成分的含盐粘土沉积中.卤水和沉积物234 U/238U比值是盐湖铀源及铀含量水平的有效指示标志之一.     

230Th/234U dating of Holocene tufas: possibilities and problems

High-resolution chronologies in continental carbonate deposits such as tufas are required for detailed palaeoclimatic and environmental studies. This work set out to establish if high-resolution U-series dating of detritus-rich Holocene tufas is routinely possible. The study centres on a paludal Holocene tufa from southern England that already has an existing Holocene chronology, based on ¹⁴C and supported by biostratigraphy, against which to compare U-series dates. The results show that significant detrital contamination combined with low initial U concentrations, and short time for ingrowth of radiogenic ²³⁰Th make high-resolution U-series dating of Holocene tufa very difficult. Moreover, a single (²³⁰Th/²³²Th)_initial value to correct for the presence of detrital ²³⁰Th is not appropriate at the study site, a finding that may apply to most Holocene tufas. Total sample dissolution of coeval samples demonstrates considerable variability in the isotopic composition of the detritus. The total sample dissolution data are too scattered to constrain chronologies at the required resolution and may indicate the incorporation of a ²³⁰Th-rich component in the detritus.     

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.     

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.     

Electron spin resonance (ESR) and thermal ionization mass spectrometric (TIMS) 230Th/234U dating of teeth in Middle Paleolithic layers at Amud Cave,Israel

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.     

Application of226Ra,228Ra,223Ra, and224Ra in coastal waters to assessing coastal mixing rates and groundwater discharge to oceans

The fate of dissolved material delivered to the coastal ocean depends on its reactivity and the rate at which it is mixed offshore. To measure the rate of exchange of coastal waters, we employ two short-lived radium isotopes,²²³Ra and²²⁴Ra. Along the coast of South Carolina, shore-perpendicular profiles of²²³Ra and²²⁴Ra in surface waters show consistent gradients which may be modeled to yield eddy diffusion coefficients of 350–540 m²s⁻¹. Coupling the exchange rate with offshore concentration gradients yields estimates of offshore fluxes of dissolved materials. For systems in steady state, the offshore fluxes must be balanced by new inputs from rivers, groundwater, sewers or other sources. Two tracers that show promise in evaluating groundwater input are barium and²²⁶Ra. These tracers have high relative concentrations in the fluids and low-reactivity in the coastal ocean. Applying the eddy diffusion coefficients to the offshore gradient of²²⁶Ra concentration provides an estimate of the offshore flux of²²⁶Ra. Measuring the concentrations of²²⁶Ra in subsurface fluids provides an estimate of the fluid flux necessary to provide the²²⁶Ra. These estimates indicate that the volume of groundwater required to support these fluxes is of the order of 40% of the surface water flow.     

An improved method for Ra isotope (226Ra, 228Ra, 224Ra) measurements by gamma spectrometry in natural waters: application to CO2-rich thermal waters from the French Massif Central

An improved method was developed to measure ²²⁶Ra, ²²⁸Ra and ²²⁴Ra in freshwaters by gamma spectrometry. Radium was selectively extracted from acidified samples using specific filters (3M EMPORE™ Radium Rad disks). The latter was subsequently analysed by gamma spectrometry. Simultaneous and direct determination of the activities of the three isotopes was performed by comparison of gamma rays of the Radium Rad disks with those of a calibrated standard disk. This efficient and reliable method allowed a reduction of sample processing to a few hours.This technique was applied to analyse the Ra isotope compositions of several CO₂-rich hydrothermal springs of the western border of the Limagne graben (French Massif Central). The studied springs emerge from a succession of granitic outcrops lined up along a major fault. Their chemical compositions evolve from calcic and magnesian chloro-bicarbonated to sodic bicarbonated. All the springs display high Ra activities, probably linked to high CO₂ content and/or high cation content of these waters, with various Ra isotope ratios. ²²⁶Ra activity ranges from 588 to 2287 mBq/l and ²²⁸Ra activity from 260 to 1590 mBq/l, whereas ²²⁴Ra displays an activity between 245 and 1808 mBq/l. Four of the six analysed springs have (²²⁸Ra/²²⁶Ra) activity ratios lower than 0.7, thus, significantly lower than the ratio expected from an interaction with a calc-alkaline granitoid (typically having (²³²Th/²³⁸U) activity ratio between 1 and 2). Low (²²⁸Ra/²²⁶Ra) ratio (0.27) of the northern water (Montpensier) suggests the existence in this area of a zone of U concentration, possibly resulting from U mobilization and accumulation induced by previous hydrothermal events. The (²²⁴Ra/²²⁸Ra) ratios display smaller variations. They suggest short transit times from the zone of Ra leaching to the surface (a few days) or a very shallow addition of ²²⁴Ra (e.g., from a localised zone where ²²⁸Th could be preferentially adsorbed on the mineral surfaces). In some cases, these ratios might be used to infer differences in transit times of waters between neighboring springs.     

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.     

Ba, Ra, Th, and U in marine mollusc shells and the potential of Ra/Ba dating of Holocene marine carbonate shells

The geochemistry of Ba, Ra, Th, and U and the potential of using ²²⁶Ra/Ba ratios as an alternative dating method are explored in modern and Holocene marine mollusc shells. Five modern shells of the Antarctic scallop Adamussium colbecki collected from the present day beach and six radiocarbon dated specimens from Holocene beach terraces of the Ross Sea region (Antarctic) between 700 and 6100 calibrated yr BP old have been analysed by mass spectrometry. In clean shells ²²⁶Ra concentrations and ²²⁶Ra/Ba ratios show a clear decrease with increasing age, suggesting the possibility of ²²⁶Ra dating. Limiting factors for such dating are Ba and ²²⁶Ra present in surface contaminants, and ingrowth of ²²⁶Ra from U present within the shell. Surface contamination is difficult to clean off entirely, but moderate levels of residual contamination can be corrected using ²³²Th. Sub-samples from the same shell with different proportions of contamination form a mixing line in a ²²⁶Ra/Ba-²³²Th/Ba graph, and the ²²⁶Ra/Ba of the pure shell can be derived from the intercept on the ²²⁶Ra/Ba axis. Contaminant corrected ²²⁶Ra/Ba ratios of late-Holocene ¹⁴C-dated samples fall close to that expected from simple ²²⁶Ra excess decay from seawater ²²⁶Ra/Ba values. ²²⁶Ra ingrowth from U incorporated into the shell during the lifetime of the mollusc can be corrected for. However, the unknown timing of post mortem U uptake into the shell makes a correction for ²²⁶Ra ingrowth from secondary U difficult to achieve. In the A. colbecki shells, ²²⁶Ra ingrowth from such secondary U becomes significant only when ages exceed ∼2500 yr. In younger shells, ²²⁶Ra/Ba ratios corrected for surface contamination provide chronological information. If evidence for a constant oceanic relationship between ²²⁶Ra and Ba in the ocean can be confirmed for that time scale, the ²²⁶Ra/Ba chronometer may enable the reconstruction of variability in sea surface ¹⁴C reservoir ages from mollusc shells and allow its use as a paleoceanographic tracer.     

Factors controlling the groundwater transport of U, Th, Ra, and Rn

A model for the groundwater transport of naturally occurring U, Th, Ra, and Rn nuclides in the²³⁸U and²³²Th decay series is discussed. The model developed here takes into account transport by advection and the physico-chemical processes of weathering, decay, α-recoil, and sorption at the water-rock interface. It describes the evolution along a flowline of the activities of the²³⁸U and²³²Th decay series nuclides in groundwater. Simple sets of relationships governing the activities of the various species in solution are derived, and these can be used both to calculate effective retardation factors and to interpret groundwater data. For the activities of each nuclide, a general solution to the transport equation has been obtained, which shows that the activities reach a constant value after a distance ϰ_i, characteristic of each nuclide. Where ϰ_i is much longer than the aquifer length, (for²³⁸U,²³⁴U, and²³²Th), the activities grow linearly with distance. Where gKⁱ is short compared to the aquifer length, (for²³⁴Th,²³⁰Th,²²⁸Th,²²⁸Ra, and²²⁴Ra), the activities rapidly reach a constant or quasi-constant activity value. For²²⁶Ra and²²²Rn, the limiting activity is reached after 1 km. High δ²³⁴U values (proportional to the ratio^ɛ234Th/^W238U) can be obtained through high recoil fraction and/or low weathering rates. The activity ratios²³⁰Th/²³²Th,²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra have been considered in the cases where either weathering or recoil is the predominant process of input from the mineral grain. Typical values for weathering rates and recoil fractions for a sandy aquifer indicate that recoil is the dominant process for Th isotopic ratios in the water. Measured data for Ra isotope activity ratios indicate that recoil is the process generally controlling the Ra isotopic composition in water. Higher isotopic ratios can be explained by different desorption kinetics of Ra. However, the model does not provide an explanation for²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra activity ratios less than unity. From the model, the highest²²²Rn emanation equals 2ɛ. This is in agreement with the hypothesis that²²²Rn activity can be used as a first approximation for input by recoil (Krishnaswamiet al 1982). However, high²²²Rn emanation cannot be explained by production from the surface layer as formulated in the model. Other possibilities involve models including surface precipitation, where the surface layer is not in steady-state.