Use of 234U/238U disequilibrium in measuring chemical weathering rate of rocks

The rate of chemical weathering of rocks has been determined by using uranium as a natural isotopic tracer. The concentration of uranium and ²³⁴U/²³⁸U ratio in natural waters, rocks, and soils of the Preto river basin (Bahia State, Brazil) was measured by alpha-ray spectroscopy.The activity ratio U234/U238 measured in the various samples indicates the uranium fraction which is dissolved from rocks during the weathering process. The results obtained show that 1 m of rock needs 25,000 yr to be weathered in this region under present climatic conditions.     

北京平原区晚中生代安山岩锆石U-Pb年代学及其地质意义

本文对北京平原区Jr173井和Jr176井安山岩进行了SHRIMP和LA-LCP-MS锆石U-Pb定年,用以精确限定北京平原区火山岩时代、盆地形成与地貌转变之间的关系。2个安山岩中的锆石多晶型良好,具有典型的生长环带和较高的Th/U比值,显示其为岩浆锆石。Jr173井底部安山岩14颗锆石的206Pb/238U年龄可分为两组,其加权平均年龄分别为122.6Ma和138.4Ma;Jr176底部安山岩53颗锆石的206Pb/238U加权平均年龄为122.63Ma,表明该期火山岩的形成时代为早白垩世晚期,与前人认为的侏罗纪有较大区别。结合前人资料,北京地区沿着黄庄-高丽营断裂一线形成断陷盆地,西部隆升为山脉,东部下降为平原,就其安山岩喷发时代、空间展布和盆地发育特征而言,可视为中国东部晚中生代构造演化的一个缩影。     

西昆仑上其汗地区火山岩LA-ICP-MS锆石U-Pb年龄及构造意义

西昆仑上其汗地区火山岩的时代及归属一直存在争议。利用LA-ICP-MS锆石U-Pb定年法对该区火山岩中霏细岩进行了测年。阴极发光图像显示,锆石发育对称的生长震荡环带结构,Th/U大部分大于0.4,显示岩浆锆石的特征。测得火山岩的²⁰⁶Pb/²³⁸U加权平均年龄为(335±4.2) Ma,形成时代为石炭纪,可将其划为阿羌岩组。结合区域地质背景资料,该火山岩可能形成于裂谷环境。     

(极)年轻火山岩激光熔蚀40Ar/39Ar定年

对中国大量年轻或/和极年轻火山岩的定年实践研究表明,(极)年轻火山岩的激光熔蚀40Ar/39 Ar定年具有不同于第四纪以前喷发火山岩定年的显著特点.激光熔蚀40Ar/39Ar定年技术因为本底低、样品用量小以及与现代惰性气体同位素质谱设备在灵敏度、高精度方面的相一致,在年轻火山岩的定年中得到深入运用.借助激光在年轻或/和极年轻火山岩的40 Ar/39 Ar定年中,实践证明,样品形成时限越年轻(特别是相当于第四纪时期的样品),Nier值与样品中初始氩比值的偏离会引起K-Ar和40Ar/39 Ar表观年龄的偏差越大.对于小于0.2Ma的样品,Nier值与样品中初始氩比值的偏离对K-Ar和40Ar/39Ar表观年龄的偏差影响呈指数增长;当样品年龄相对较老(老于第四纪)时,Nier值和初始氩比值的偏离对K-Ar和40Ar/39 Ar表观年龄的影响较小.以40Ar/ArAr定年为出发点,定量给出界定年轻与极年轻火山岩的年龄:2～0.2Ma的火山岩界定为年轻火山岩,0.2Ma以来的火山岩称为极年轻火山岩.实验结果还证实,测定(极)年轻火山岩基质年龄时要尽量剔除非同源分馏的斑晶,以便去除斑晶可能带来的过剩氩影响;年轻火山岩样品的测年,应根据岩石结构和粒度特征选取合适的粒度,通常情况下,推荐0.2mm颗粒直径(60～80目)为理想粒径;年轻火山岩样品在快中子辐照后冷却放置时间不宜过长,否则造成37 Ar测不准,影响数据结果,带来较大偏差;激光40Ar/39Ar精细定年对标准样品的均一性有很高的要求,通过标定常用的国内外监测标样发现,标样SB-778-Bi,Bem4M,BT-1均一性很好,适合用作激光熔蚀40Ar/39Ar定年监测;测试数据的处理中,火山岩喷发后冷却结晶中同时形成的斑晶和基质的等时线处理能够帮助获得客观真实和精细的年龄结果.在此基础上,北京大学惰性气体同位素实验室建成了专用于(极)年轻火山岩精细定年的激光熔蚀40Ar/39Ar定年实验流程.     

新疆铁木尔特铅锌铜矿床锆石U-Pb和黑云母40Ar/39Ar年代学及其矿床成因意义

新疆铁木尔特铅锌铜矿床位于阿尔泰造山带南缘克兰盆地内,矿体呈脉状产于康布铁堡组火山岩地层中.为准确厘定其成岩成矿时代,作者分别对矿区赋矿火山岩和含矿石英脉中的云母进行了年龄测定,获得2件火山岩样品的锆石LA-ICP-MS U-Pb年龄分别为396±5Ma和405±5Ma,2件黑云母样品的40 Ar/39 Ar坪年龄分别为240±2Ma和235±2Ma,相应的39Ar/36Ar-40Ar/36Ar等时线年龄分别为238±3Ma和233±3Ma,与坪年龄在误差范围内一致.据此,认为矿区内康布铁堡组火山岩形成于396～405 Ma,成矿作用发生于235～240Ma;成岩年龄早于成矿年龄约165Ma.因此,铁木尔特铅锌铜矿为典型的后生矿床,而不可能是同生VMS型矿床.考虑到成矿年龄稍晚于区域大规模变质作用(约250Ma),推测成矿作用与阿尔泰造山带碰撞造山作用有关.结合矿床地质特征和流体包裹体特征,认为铁木尔特铅锌铜矿为典型的陆陆碰撞体制下形成的造山型矿床.     

Geochemical evolution of a shallow magma plumbing system during the last 500 years, Miyakejima volcano, Japan: Constraints from U-Th-Ra systematics

In order to unravel magma processes and the geochemical evolution of shallow plumbing systems beneath active volcanoes, we investigated U-series disequilibria of rocks erupted over the past 500 years (1469-2000 AD) from Miyakejima volcano, Izu arc, Japan. Miyakejima volcanic rocks show ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with excess ²³⁸U and ²²⁶Ra, due to the addition of slab-derived fluids to the mantle wedge. Basaltic bombs of the 2000 AD eruption have the lowest (²³⁰Th/²³²Th) ratio compared to older Miyakejima eruptives, yielding the youngest ²³⁸U-²³⁰Th model age of 2 kyr. This reinforces our previous model that fluid release from the slab and subsequent magma generation in the mantle wedge beneath Miyakejima occur episodically on a several-kyr timescale. In the last 500 years, Miyakejima eruptives show: (1) a vertical trend in a (²³⁰Th/²³²Th)-(²³⁸U/²³²Th) diagram and (2) a positive linear correlation in a (²²⁶Ra/²³⁰Th)₀ − 1/²³⁰Th diagram, which is also observed in lavas from some of the single eruptions (e.g., 1940, 1962, and 1983 AD). The variations cannot be produced by simple fractional crystallization in a magma chamber with radioactive decay of ²³⁰Th and ²²⁶Ra, but it is possibly produced by synchronous generation of melts in the mantle wedge with different upwelling rate or addition of multiple slab-derived fluids. A much more favorable scenario is that some basaltic magmas were intermittently supplied from deep in the mantle and injected into the crust, subsequently modifying the original magma composition and producing variations in (²³⁰Th/²³²Th) and (²²⁶Ra/²³⁰Th)₀ ratios via assimilation and fractional crystallization (AFC). The assimilant of the AFC process would be a volcanic edifice of previous Miyakejima magmatism. Due to the relatively short timescales involved, the interaction between the assimilant and recent Miyakejima magmatism has not been recorded by the Sr-Nd-Pb isotopic systems. In such cases, Th isotopes and (²²⁶Ra/²³⁰Th) ratio are excellent geochemical tracers of magmatic evolution.     

琼北火山岩激光40Ar/39Ar定年研究

新生代以来,雷琼地区多次、大量地喷发了一系列火山岩。前人主要基于K-Ar法对此划分了期次。本文采用激光40Ar/39Ar年代学方法,对琼北火山岩区进行了精细定年研究。低本底激光40Ar/39Ar法能够对低钾含量,极少量样品(毫克级)进行精细测定,非常适合极年轻火山岩的定年工作。结果显示的火山岩激光40Ar/39Ar法高质量数据表明琼北火山喷发活动时限跨越1.3～0.052Ma。在比较了表观年龄与等时线年龄差异之后,本文给出了年龄推荐值。正如测试数据所显示,本地区新生代火山岩普遍存在40Ar和36Ar过剩的问题,此时只有等时线年龄才代表喷发的真实年龄。     

雷州半岛第四纪火山岩激光40Ar/39Ar等时线定年研究

雷州半岛是我国新生代火山岩最重要的分布地区之一,火山活动主要集中在中晚更新世。前人对雷州火山岩的年代学研究以K-Ar法为主。研究表明,雷州火山岩测年结果大致分布在0.38～3.04Ma范围内。根据地层和火山岩层的叠置关系,雷州第四纪火山岩由于覆盖在被确定是1.87Ma和0.76Ma沉积的地层之上,故火山岩年龄应小于该地层年龄。K-Ar法定年结果与雷州地区地层叠置关系存在矛盾。本文通过对雷州半岛第四纪火山岩进行野外考察及采样,利用激光40Ar/39Ar年代学方法进行了精细定年。结果表明,雷州火山岩的喷发主要集中18万年前后。定年结果还表明,对于年轻样品,基于尼尔值计算的K-Ar年龄及40Ar/39Ar表观年龄偏老,等时线年龄相对较为可靠。对同一样品的斑晶、基质作斑晶-基质等时线计算,只有在斑晶基质满足同源条件时才有意义。本文首次提出,通过对比未照射样品的初始36Ar/38Ar值的均一性,以检验样品是否同源,确认斑晶-基质等时线年龄的可信度。据此,等时线的处理方法可以推广应用于特定区域内全部同源同时样品。     

西天山查岗诺尔和智博铁矿区火山岩地球化学特征、锆石U-Pb年龄及地质意义

西天山东段的查岗诺尔铁矿和智博铁矿赋存于以玄武岩、玄武安山岩、粗面岩以及安山质凝灰岩为主的晚石炭世火山岩中, 对火山岩的形成时代以及构造地质背景的研究是重建成矿过程的关键。本文通过对两个矿区的火山岩进行岩石地球化学和LA-ICP-MS锆石U-Pb测年分析来探讨火山岩形成的构造环境与时代。地球化学分析表明大多数火山岩化学成分从钙碱性、高钾钙碱性变化到钾玄岩系列,富集轻稀土元素(LREE)和大离子亲石元素(LILE; 如Rb、Th、K),重稀土元素(HREE)配分平坦,同时具有Nb、Ta、Ti的强烈亏损,类似于岛弧火山岩的地球化学特征。大多数玄武质火山岩在构造环境判别图中位于火山弧环境。LA-ICP-MS锆石U-Pb测年显示流纹岩和英安岩的²⁰⁶Pb/²³⁸U加权平均年龄分别为301.8±0.9Ma和300.3±1.1Ma。此外,对两件闪长岩样品测年获得²⁰⁶Pb/²³⁸U加权平均年龄介于303.8～305Ma之间。火山岩与闪长岩样品具有类似的地球化学特征以及形成时代,表明它们可能来源于同一母岩浆,形成于相同的构造背景下。结合区域地质资料,本文认为矿区内出露的高钾钙碱性到钾玄岩系列火山岩可能属于俯冲过程末期阶段大陆岛弧岩浆作用的产物。     

Zircon U-Pb Geochronology and Geochemical Characteristics of the Volcanic Host Rocks from the Tongyu VHMS Copper Deposit in the Western North Qinling Orogen and Their Geological Significance

Precise in situ zircon U-Pb dating and Lu–Hf isotopic measurement using an LA-ICP-MS system, whole-rock major and trace element geochemistry and Sr–Nd isotope geochemistry were conducted on the volcanic host rocks of the Tongyu copper deposit on the basis of further understanding of its geological characteristics. Three zircon samples from the volcanic host rocks yielded 206Pb/238 U weighted average ages ranging from 436±4 Ma to 440±5 Ma, which are statistically indistinguishable and coeval with the ca. 440 Ma northward subduction event of the Paleo-Qinling oceanic slab. The volcanic host rocks were products of magmatic differentiation that evolved from basalt to andesite to dacite to rhyolite, forming an integrated tholeiitic island arc volcanic rock suite. The primitive mantle-normalized trace element patterns for most samples show characteristics of island arc volcanic rocks, such as relative enrichment of LILE(e.g. Th, U, Pb and La) and depletion of HFSE(e.g. Nb, Ta, Ti, Zr and Hf). Discrimination diagrams of Ta/Yb vs Th/Yb, Ta vs Th, Yb vs Th/Ta, Ta/Hf vs Th/Hf, Hf/3 vs Th vs Nb/16, La vs La/Nb and Nb vs Nb/Th all suggest that both the volcanic host rocks from the Tongyu copper deposit and the volcanic rocks from the regional Xieyuguan Group were formed in an island arc environment related to subduction of an oceanic slab. Values of ISr(0.703457 to 0.708218) and εNd(t)(-2 to 5.8) indicate that the source materials of volcanic rocks from the Tongyu copper deposit and the Xieyuguan Group originated from the metasomatised mantle wedge with possible crustal material assimilation. Most of the volcanic rock samples show good agreement with the values of typical island arc volcanic rocks in the ISr-εNd(t) diagram. The involvement of crustal-derived material in the magma of the volcanic rocks from the Tongyu copper deposit was also reflected in the zircon εHf(t) values, which range from-3.08 to 10.7, and the existence of inherited ancient xenocrystic zircon cores(2616±39 Ma and 1297±22 Ma). The mineralization of the Tongyu copper deposit shows syn-volcanic characteristics such as layered orebodies interbedded with the volcanic rock strata, thus, the zircon U-Pb age of the volcanic host rocks can approximately represent the mineralization age of the Tongyu copper deposit. Both the Meigou pluton and the volcanic host rocks were formed during the ca. 440 Ma northward subduction of the Paleo-Qinling Ocean when high oxygen fugacity aqueous hydrothermal fluid released by dehydration of the slab and the overlying sediments fluxed into the mantle wedge, triggered partial melting of the mantle wedge, and activated and extracted Cu and other ore-forming elements. The magma and ore-bearing fluid upwelled and erupted, and consequently formed the island arc volcanic rock suite and the Tongyu VHMS-type copper deposit.     

Fixation of radionuclides in the 238U decay series in the vicinity of mineralized zones: 1. The Austatom Uranium Prospect,Northern Territory,Australia

The minimum age of a zone of secondary uranium mineralization, located at the Austatom Prospect in the Alligator Rivers region of Australia, is estimated to be 3.6 × 10⁵y. This is derived from a geochronological model based on retarded leaching of ²³⁴U with respect to ²³⁸U and on ratios within the ore of these members of the ²³⁸U decay series. Although kaolinite is a dominant mineral in the weathered schist-host-rocks, retarded dissolution of ²³⁴U occurs only in the presence of the clay minerals illite and montmorillonite. In their absence the reverse occurs. A model is proposed to explain the results. Ratios of ²³⁰Th to ²³⁸U indicate that the mineralization has probably remained stationary within the weathered schist for at least 1 to 2 × 10⁵y. Future use of clay minerals as buffers in radioactive waste repositories is supported by the excellent long-term retention obtained for oxidized uranium, probably due in part to isomorphic substitution into the clay crystal lattice.     

State of disequilibrium between 238U, 234U, 226Ra and 222Rn in groundwater from bedrock

Approximately one thousand drilled wells were investigated for their natural radioactivity. The determinations of ²³⁸U, ²³⁴U, ²²⁶Ra and ²²²Rn from 310 samples showed a high state of radioactive disequilibrium between the members of the uranium series present in water. The ${}^{238}\text{U}{}^{226}\text{Ra}$ activity ratio usually fell in the range 1–20 and the ${}^{238}\text{U}{}^{222}\text{Rn}$ activity ratio in the range 1–20 × 10^?4, the highest activity ratios being from samples with an elevated uranium content. The ${}^{234}\text{U}{}^{238}\text{U}$ activity ratio varied between 0.76 and 4.67, the most frequent values showing a 60% excess of ²³⁴U in the samples. Most of the ${}^{234}\text{U}{}^{238}\text{U}$ activity ratios near unity were found in samples with a high uranium content. Several drilled wells with anomalously high uranium contents were found in southern Finland. The average ²²⁶Ra and ²²²Rn contents of these wells were not exceptionally high, which suggests high mobility of uranium in groundwater from the areas involved.     

Precise geochronology of phoscorites and carbonatites:: The critical role of U-series disequilibrium in age interpretations

We present the results of a comparative study of several geochronometer minerals (baddeleyite, zircon, apatite, phlogopite and tetraferriphlogopite) and isotopic systems (U-Pb, Th-Pb and Rb-Sr) from phoscorites (magnetite-forsterite-apatite-calcite rocks) and carbonatites of the Kovdor ultramafic-alkaline-carbonatite massif, Kola Peninsula, Russia. Uranium, thorium and their decay products are extremely fractionated by minerals that crystallise from carbonatite and phoscorite magma. We obtain high-precision ages from different chronometers, compare their accuracy, and evaluate the role of geochronological pitfalls of initial radioactive disequilibrium, differential migration of radiogenic isotopes, and inaccurate decay constants.Apatite yielded concordant U-Th-Pb ages between 376 and 380 Ma. The accuracy of the apatite ²³⁸U-²⁰⁶Pb ages is, however, compromised by uncertainty in the amount of radiogenic ²⁰⁶Pb produced from initial excess ²³⁰Th. The ²³⁵U-²⁰⁷Pb ages are relatively imprecise due to large common Pb correction and the uncertainty in the initial Pb isotopic composition. The Th-Pb system yields a more precise age of 376.4 ± 0.6 Ma.Zircon from two carbonatite samples is characterised by moderate to low U contents, high Th contents, and very high Th/U ratios up to 9000. The ²⁰⁶Pb*/²³⁸U systems in the zircon are strongly affected by the presence of excess ²⁰⁶Pb*, produced by decay of initial ²³⁰Th. The ²⁰⁸Pb*/²³²Th ages of zircon from both carbonatite samples are uniform and yield a weighted average of 377.52 ± 0.94 Ma.Baddeleyite U-Pb analyses are 3 to 6% normally discordant and have variable ²⁰⁷Pb*/²⁰⁶Pb* apparent ages. Eleven alteration-free baddeleyite fractions from three samples with no evidence for Pb loss yield uniform ²⁰⁶Pb*/²³⁸U ages with a weighted average of 378.54±0.23 Ma (378.64 Ma after correction for initial ²³⁰Th deficiency), which we consider the best estimate for age of the phoscorite-carbonatite body of the Kovdor massif. The ²⁰⁶Pb*/²³⁸U ages of baddeleyite fractions from five other samples spread between 378.5 and 373 Ma, indicating a variable lead loss up to 1.5%. The anomalously old ²⁰⁷Pb/²³⁵U and ²⁰⁷Pb/²⁰⁶Pb ages are consistent with the presence of excess radiogenic ²⁰⁷Pb* in the baddeleyite. We interpret this as a result of preferential partitioning of ²³¹Pa to baddeleyite.Fifteen phlogopite and tetraferriphlogopite fractions from five carbonatite and phoscorite samples yielded precise Rb-Sr isochron age of 372.2 ± 1.5 Ma, which is 5 to 7 m.y. younger than our best estimate based on U-Th-Pb age values. This difference is unlikely to be a result of the disturbance or late closure of Rb-Sr system in phlogopite, but rather suggests that the accepted decay constant of ⁸⁷Rb is too high.Comparative study of multiple geochronometer minerals from the Kovdor massif has revealed an exceptional complexity of isotopic systems. Reliable ages can be understood through systematic analysis of possible sources of distortion. No single geochronometer is sufficiently reliable in these rocks. Th-Pb and Rb-Sr can be a very useful supplement to U-Pb geochronometry, but the routine use of these geochronometers together will require more precise and accurate determination of decay constants for ²³²Th and ⁸⁷Rb.     

Application of the equations of radioactive growth and decay to geochronological models and explicit solution of the equations by Laplace transformation

A recently developed method of pore-fluid age determination assumes secular equilibrium in the ²³⁸U decay chain. The efficacy of this approximation is investigated using computer evaluations of the equations that give the time evolution of the ²³⁸U decay chain, i.e. the solution of the equations of radioactive growth and decay. This analysis is performed considering two alternative geochemical scenarios to that of secular equilibrium — only ²³⁸U present initially and ²³⁸U and ²³⁴U present initially. In addition, the effects of the ²³⁵U decay chain are also determined in a similar fashion. These particular examples were chosen to show that more sophisticated geochronological models for many dating applications can be developed using such computer calculations. To facilitate such analyses, a solution of the equations of radioactive growth and decay for an arbitrary initial condition is derived using the Laplace transformation method and matrix algebra. Other solutions — both general and special — that are found in some well-known textbooks are reviewed.     

U‐Th Zircon Dating by Laser Ablation Single Collector Inductively Coupled Plasma‐Mass Spectrometry (LA‐ICP‐MS)

Zircon crystals in the age range of ca. 10–300 ka can be dated by ²³⁰Th/²³⁸U (U‐Th) disequilibrium methods because of the strong fractionation between Th and U during crystallisation of zircon from melts. Laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) analysis of nine commonly used reference zircons (at secular equilibrium) and a synthetic zircon indicates that corrections for abundance sensitivity and dizirconium trioxide molecular ions (Zr₂O₃⁺) are critical for reliable determination of ²³⁰Th abundances in zircon. When corrected for abundance sensitivity and interferences, mean activity ratios of (²³⁰Th)/(²³⁸U) for nine reference zircons analysed on five different days averaged 0.995 ± 0.023 (95% confidence weighted by data‐point uncertainty only, MSWD = 1.6; n = 9), consistent with their U‐Pb ages > 4 Ma that imply equilibrium for all intermediate daughter isotopes (including ²³⁰Th) within the ²³⁸U decay chain. U‐Th zircon ages generated by LA‐ICP‐MS without mitigating (e.g., by high mass resolution) or correcting for abundance sensitivity and molecular interferences on ²³⁰Th are potentially unreliable. To validate the applicability of LA‐ICP‐MS to this dating method, we acquired data from three late Quaternary volcanic units: the 41 ka Campanian Ignimbrite (plutonic clasts), the 161 ka Kos Plateau Tuff (juvenile clasts) and the 12 ka Puy de Dôme trachyte lava (all eruption ages by Ar/Ar, with zircon U‐Th ages being of equal or slightly older). A comparison of the corrected LA‐ICP‐MS results with previously published secondary ion mass spectrometry (SIMS) data for these rocks shows comparable ages with equivalent precision for LA‐ICP‐MS and SIMS, but much shorter analysis durations (~ 2 min vs. ~ 15 min) per spot with LA‐ICP‐MS and much simpler sample preparation. Previously undated zircons from the Yali eruption (Kos‐Nisyros volcanic centre, Greece) were analysed using this method. This yielded a large age spread (~ 45 to > 300 ka), suggesting significant antecryst recycling. The youngest zircon age (~ 45 ± 10 ka) provides a reasonable maximum estimate for the eruption age, in agreement with the previously published age using oxygen isotope stratigraphy (~ 31 ka).     

非稀释剂法电感耦合等离子体质谱测定磷灰石中铀钍钐同位素的含量

准确测定238U、232Th、147Sm同位素含量是磷灰石(U-Th)/He同位素定年方法的关键。本文建立了非稀释剂法电感耦合等离子体质谱测定磷灰石中238U、232Th和147Sm同位素含量的测定流程。该方法假定样品中的238 U、232 Th和147 Sm同位素丰度与其自然丰度是一致的,根据238 U、232 Th和147 Sm同位素的自然丰度和测得的样品中总的U、Th和Sm的含量得到样品中238U、232Th和147Sm同位素的含量。对国内玄武岩标准物质和(U-Th)/He定年法的年龄标准物质Durango磷灰石进行了总U、Th、Sm含量的测试,验证流程的可行性,结果表明玄武岩标准物质的测定值与标准值在误差范围内一致,经计算得到该磷灰石的(U-Th)/He年龄为30.0 Ma,与文献获得的该磷灰石(U-Th)/He年龄(31.02±1.01)Ma(1σ)在误差范围内一致,表明本文建立的238U、232Th和147Sm同位素含量的测定流程是可行的。对于没有稀释剂的实验室,该方法简单适用,值得推广应用。     

Preferential leaching and the age of radiation damage from alpha decay in minerals

Preferential release into solution of radionuclides that result from alpha decay is a contributor to natural isotopic disequilibrium. Such release is critical to geochemical understanding of alpha-decay products and would be an undesirable characteristic of solidified nuclear waste in deep geological formations. Spontaneous annealing of the radiation damage that is responsible for the preferential release is shown to diminish the effect in thorianite and uraninite which we have found to be 550 to 1000 M.y. old, respectively. Leaching experiments and measurements of the thorium and uranium isotopes show that there is strongly enhanced release of short-lived ²²⁸Th relative to ²³²Th, but only slight enhancement of long-lived ²³⁴U and ²³⁰Th relative to ²³⁸U and ²³²Th. These results are interpreted in terms of natural annealing of damage occurring on a time scale between the ~10 and 10⁵ years of the alpha-decay products. With a simple assumption actual times for the survival of the enhanced leaching in these minerals are ~ 15,000 years.     

Mixing and cycling of uranium,thorium and 210Pb in Puget Sound sediments

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.     

Precise two chronometer dating of Pleistocene travertine: The Th/U and Raex/Ra(0) approach

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.²²⁶Ra_ex/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 ²²⁶Ra_ex/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 ²²⁶Ra_ex/²²⁶Ra(0) ages agreed well with those derived from ²³⁰Th/²³⁴U, (ii) all data plot within uncertainty on the ²²⁶Ra_ex/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, ²²⁶Ra_ex/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.     

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.