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.     

In situ U-series dating by laser-ablation multi-collector ICPMS: new prospects for Quaternary geochronology

The capabilities and potential applications of in situ dating of Quaternary materials using laser ablation-MC-ICPMS are explored. ²³⁴U/²³⁸U and ²³⁰Th/²³⁴U can be measured with precision sufficient for dating at a spatial resolution of 100 μm or better in samples that contain as a little as 1 ppm uranium. Moreover, U and Th concentrations and U-series isotope ratios can be continuously profiled to determine changes in age that occur with sample growth (e.g. in speleothems). These capabilities additionally permit the dating of bones, teeth and possibly molluscs, which are subject to post-mortem open-system behaviour of U-series isotopes, and can be employed to elucidate processes of U-series migration during weathering and diagenesis. A drawback of laser ablation-MC-ICPMS is that it cannot in general provide U-series age estimates with the high precision and accuracy of conventional TIMS or solution MC-ICPMS methods. However, sample preparation is straightforward, the amount of sample consumed negligible, and it can be used to rapidly characterise or screen and select samples from which more precise and accurate dates can be obtained using conventional methods. Given further instrumental developments and the establishment of suitable matrix-matched standards for carbonates and other materials, we foresee that laser ablation-MC-ICPMS will play an increasingly important role in Quaternary dating research.     

Models of diffusion-limited uptake of trace elements in fossils and rates of fossilization

Many fossils are assumed to take up trace elements by a process of combined diffusion plus adsorption (DA), yet in principle composition profiles can be explained by several different diffusion-limited processes, including diffusion plus reaction or recrystallization (DR) and double-medium diffusion (DMD). The DA and DMD models are supported by REE and U composition profiles across fossil teeth, measured by laser-ablation ICP-MS, that show error-function - like diffusion profiles into enamel from the dentine-enamel interface and concentrations in the interior of enamel that are at original biogenic levels or higher. Published composition and age profiles in some Pleistocene bones may be better explained by a DR model. All three diffusion models imply linear behavior between age and distance squared, vastly simplifying U-series dating methods for Pleistocene fossils. Modeled uptake rates for fossil teeth yield a strict minimum bound on durations of about one decade to one century. The similarity of diffusion profiles in teeth, irrespective of depositional ages ranging from ∼30 ka to >30 Ma, implies that uptake occurred quickly, with a maximum duration of a few tens of kyr for typical fossil enamel; faster uptake is implied for typical fossil bone and dentine. Disparities in these uptake estimates compared to some archeological bone may reflect sampling and preservation bias for paleontological vs. archeological materials.     

U–Pb dating of detrital zircons for sediment provenance studies—a comparison of laser ablation ICPMS and SIMS techniques

New developments in U–Pb dating of zircons by laser ablation (LA) ICPMS are described and, for the first time, a direct comparison of detrital zircons dated by LA ICPMS and SIMS methods is presented. True real-time mass bias correction is made by aspirating a Tl/U tracer at the same time as laser ablation. The method is similar to that described in Horn et al. (2000), except that enriched ²³³U rather than ²³⁵U is used in the tracer solution. Correction for laser-induced Pb/U elemental fractionation is based on a mathematical treatment of time-resolved data that is independent of laser ablation characteristics and does not require external standardisation. Internal corrections for mass bias and elemental fractionation eliminate the effects of variable sample matrix on isotopic ratios and improve the accuracy of U–Pb dating by laser ablation ICPMS. With the proper error propagation, the precision of U–Pb age determinations is only slightly worse than SIMS-based ion probe dating. However, LA ICPMS is capable of much more rapid analysis of the large number of zircons required for sediment provenance studies. There is excellent agreement between concordant laser ablation ICPMS and SIMS analyses of detrital zircons extracted from lower Silurian metasandstone from the Ulven Group (Skarfjell Formation) in the west Norwegian Caledonian nappes. Both LA ICPMS and SIMS U–Pb zircon ages indicate that sedimentary detritus of the Ulven Group was supplied from a terrain containing zircons of Archean, Proterozoic and early Ordovician age.     

A test of uranium-series dating of fossil tooth enamel: results from Tournal Cave,France

A series of well preserved mammal bones and horse teeth was analyzed from archaeological levels of Tournal Cave (Magdalenian, Aurignacian, and Mousterain) to test the hypothesis that well-crystallized enamel behaves more as a closed system than does whole bone. The isotopic composition of bones and tooth enamels from this deposit meet criteria for confidence, and gave no reasons to suspect contamination or open-system behavior. Two samples for which²³¹Pa could be analyzed showed internal concordance with the respective²³⁰Th ages. In spite of the favourable isotopic criteria, however, comparison of the U-series ages of the bones and the tooth enamel with stratigraphic position and¹⁴C control indicated the dates were not meaningful. In general, both bones and tooth enamels gave ages too young, although some were clearly too old. Neither group showed any systematic increase of age with stratigraphic depth. Tooth enamel, therefore, shows no advantage over bone for U-series dating for this site. In Tournal cave both bones and enamel are apparently open to U, which is probably cycling as a consequences of post-depositional groundwater movement.     

第四纪骨化石样品的多方法对比测年

本文报道作者用¹⁴C、铀系和ESR等多种测年技术对比测定第四纪骨化石样品年龄结果,对比分析骨化石中各含碳组分¹⁴C年龄的异同。在此基础上讨论诸测年方法的可靠性和测年精度,分析哪种含碳组分最能代表骨质样品的真实年龄。对晚于40 000aB.P.的骨质样品,作者倾向于样品中氨基酸的¹⁴C测年,而对更老的样品,铀系法应优先被选用。本文还对北京周口店山顶洞遗址骨化石样品中不同含碳组分的¹⁴C测年结果做了讨论。     

Differential diagenesis of strontium in archaeological human dental tissues

The investigation of prehistoric human migration from the measurement of Sr-isotope ratios within preserved tissue is critically dependent on the preservation of biogenic Sr. A number of recent studies have involved isotope ratio measurements on samples of archaeological tooth and bone, but doubt remains as to the extent of diagenesis in various skeletal tissues and the effectiveness of procedures designed to decontaminate them. The authors have compared Sr abundance and isotope ratios in enamel and dentine from archaeological teeth in order to assess the integrity of the biogenic Sr signal preserved within the respective tissues. It is concluded that enamel appears, in most cases, to be a reliable reservoir of biogenic Sr, but that dentine, and by implication bone, is not. The diagenesis of dentine is highly variable even between burials within a single site. For the majority of teeth, dentine diagenesis was not simply by addition of soil-derived Sr, but involved substantial, sometimes complete, turnover of the original biogenic material. It is suggested that, for most of the samples investigated, current decontamination techniques may not have been effective in isolating biogenic Sr from dentine. Similar considerations are likely to apply to archaeological and fossil bone, but the possibility arises to use dentine and enamel measurements to assess the effectiveness of decontamination procedures which may then be used for bone.     

文石-方解石石笋U/Th体系的封闭性判断及意义

湖南省龙山县莲花洞两根大型石笋LLl(文石-方解石型)和LL5(文石型)ICP-MS230Th结果表明,82个年龄数据并不完全符合石笋生长层序律.根据U/Th同位素比值、沉积和矿物学特征,分析了同位素体系开放度对建立石笋正确年代学模式的影响.莲花洞LLl石笋全新世以来234U/238U对230Th/238U的比值具有谐和性特征并且230Th年龄层序正常,说明文石矿物基本接近U/Th同位素封闭系统,实测年龄基本可靠.10～40 ka期间234U/238U与230Th/238U离散度较大和矿物具有溶蚀、风化现象,表明体系发生U加入/流失作用.LL5石笋60～80 ka期间封闭性较好,实测年龄可信.上述结果表明,同一洞穴中文石石笋U/Th同位素体系开放度与时间的关系并不是线性关系,沉积时水文和物理化学性质以及随后的保存状况是决定洞穴文石石笋同位素封闭性的关键因素.     

激光剥蚀等离子质谱微区分析在固体地球科学中的应用进展

当前分析化学技术正向着痕量微区方向发展。这使得我们能够用更小更少的样品直接得到更多的地球化学信息。在诸多微区测试技术中,激光剥蚀等离子质谱（LA-ICPMS）技术发展最快。其地质应用较广,激光探针等离子体质谱能够进行固体样品的微区微量元素和同位素的分析,具有灵敏度高、简便、快速的特点,同样具有在同位素定年上的潜力。近年来又研制出激光剥蚀多道接收等离子质谱（LA-MC-ICPMS）仪,使得微区同位素分析开始了新的革命。而多种微区技术综合应用为近几年分析地球化学新的趋势。     

同位素稀释热电离质谱法测定锡石U-Pb年龄探索

针对我国锡多金属矿床的定年问题,建立一种采用同位素稀释热电离质谱(ID-TIMS)法进行锡石U-Pb同位素定年的方法,并与激光烧蚀电感耦合等离子体质谱(LA-ICP-MS)法进行对比验证。由于采用化学处理技术分别纯化了U和Pb,减少了普通铅的影响,大大提高了分析测定精度。将该方法应用于某地区石英-锡石-黑钨矿脉的锡石样品分析,获得了精确的U-Pb年龄值。     

电子自旋共振（ESR）化石测年研究

对ＥＳＫ测年样品的累积剂量和剂量率测量进行了讨论，并对化石样品年龄及其误差计算模式进行了探讨。对北京猿人洞牙化石釉质层的铡年研究表明，年龄数据稳定可靠，可与有关测年法结果对比。ＥＳＲ化石测年法已成为当前唯一能直接测定化石年龄大于４０万年的测年方法，对古人类演化研究具有重大意义。     

A method for coupled ESR/U-series dating of teeth showing post-depositional U-loss

An additional method of coupled ESR/U-series dating is developed for teeth showing post-depositional U-loss. The fundamental parameter for the dose rate calculation is the present-day ²³⁰Th-activity because of the geochemical immobility of thorium. Uranium and thorium concentrations are measured by thermal ionization mass spectrometry (TIMS). Due to the unknown uranium history an average saturation uptake of uranium is assumed leading to an average development of U-series activities. Therewith an internal dose rate and the age T can be calculated on condition that the modelled ²³⁰Th-activity at time T corresponds with the measured value. Using this new method, teeth, found in archaeological sites in France (Gramat, Bramefond), could be dated even though they show U-loss after U-uptake. Two teeth from Gramat could be dated to 128.3±8.6 and 130.5±10 ka. Two teeth from Bramefond have ages of 104.4±8.4 and 115.1±10.2 ka. Both sites can be ascribed to oxygen isotope stage 5.     

Lead isotope evidence for recent uranium mobility in geological formations of Brazil: implications for radioactive waste disposal

Lead–lead isotope data from whole rock samples are used to investigate the recent (last few million years) mobility of U and Th. The method is based on the comparison of the calculated present day U and Th concentrations required to yield the Pb isotope composition in the samples with the actual present day concentrations of U and Th obtained by direct measurement. The geological formations studied include the Neoproterozoic carbonate sediments of the Bambuı́ Group, Archean/Paleoproterozoic granite–greenstone terrain of the Contendas–Mirante Complex and a Proterozoic ortho-gneisses hosting U deposit in Lagoa Real. All these formations are in the São Francisco Craton, Brazil. The data show high U mobility in the carbonate sediments and in the deformed ortho-gneisses set in a ductile shear zone. Infiltration of groundwater through fault zones seems to have facilitated the U mobility. The Pb isotope approach is a useful technique complementing U-series disequilibrium studies and may be included for site characterization studies for radioactive waste disposal.     

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.     

洞穴地点骨化石铀系年龄可信度的讨论*

骨化石是铀不平衡系测年法广泛应用而又颇有争议的研究对象。文章通过对典型铀加入模式的计算,指出以α能谱的精度,二种铀系年龄差异的显著性表明近期内有较大量铀的迁移,但其在误差范围内的一致不能保证样品构成封闭体系。以往积累的数据表明,大多数洞穴地点骨化石给出了二法一致的铀系年龄,但钙板与下伏骨化石铀系年龄大多差异显著且与地层顺序矛盾,即使被次生碳酸盐岩包裹,多半骨化石的铀系年龄仍显著偏低于其包裹体。此外,相当一部分样品的U-Th同位素比难以用简单的铀后期加入或淋失来解释。基于对次生碳酸盐岩铀系年龄可信度的认识,骨化石总体上不构成封闭体系,所载铀系年代信息只具有限的分辨率。     

High resolution (5 μm) U–Th–Pb isotope dating of monazite with excimer laser ablation (ELA)-ICPMS

Monazite [(LREE)PO₄], a common accessory mineral in magmatic and metamorphic rocks, is complementary to zircon in U–Th–Pb geochronology. Because the mineral can record successive growth phases it is useful for unravelling complex geological histories. A high spatial resolution is required to identify contrasted age domains that may occur at the crystal-scale. Bulk mineral techniques such as ID-TIMS, applied to single monazite grains recording multiple overgrowths or isotope resetting can result in partly scattered discordant analytical points that produce inaccurate intercept ages. Laser ablation (LA)-ICPMS has been demonstrated to be a useful technique for U–Th–Pb dating of zircons, and this study tests its analytical capabilities for dating monazite. A sector field high resolution ICPMS coupled with a 193 nm ArF excimer laser ablation microprobe is capable of achieving a high spatial resolution and producing stable and reliable isotope measurements.

The U–Th–Pb systematic was applied to monazite grains from several samples: a lower Palaeozoic lens from high-grade terrains in Southern Madagascar, Neogene hydrothermal crystals from the Western Alps, a Palaeoproterozoic very high temperature granulite from central Madagascar and a Variscan leucogranite from Spain, directly on a polished thin section. The major aim was to compare and/or reproduce TIMS and EMP ages of monazite from a variety of settings and ages. The three independent ²⁰⁶Pb/²³⁸U, ²⁰⁷Pb/²³⁵U and ²⁰⁸Pb/²³²Th ratios and ages were calculated. Isotope fractionation effects (mass bias, laser induced fractionation) were corrected using a chemically homogeneous and U–Pb concordant monazite as external standard.

This study demonstrates that excimer laser ablation (ELA)-ICPMS allows U–Th–Pb dating of monazite with a high level of repeatability, accuracy and precision as well as rapidity of analysis. A spatial resolution almost comparable to that of EMP in terms of crater width (5 μm) produced precise ²⁰⁸Pb/²³²Th, ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ratios for dating Palaeozoic to Precambrian monazites. The advantages of (ELA)-ICPMS isotope dating are precision, accuracy and the ability to detect discordance. In the case of late Miocene hydrothermal monazites from the Alps, a larger spot size of 25 μm diameter is required, and precise and accurate ages were obtained only for ²⁰⁸Pb/²³²Th systematics. Results from the Variscan granite show that in situ U–Th–Pb dating of monazites with (ELA)-ICPMS is possible using a 5 μm spot directly on thin sections, so that age data can be placed in a textural context.     

The effect of tissue structure and soil chemistry on trace element uptake in fossils

Trace element profiles for common divalent cations (Sr, Zn, Ba), rare-earth elements (REE), Y, U, and Th were measured in fossil bones and teeth from the c. 25 ka Merrell locality, Montana, USA, by using laser-ablation ICP-MS. Multiple traverses in teeth were transformed into 2-D trace element maps for visualizing structural influences on trace element uptake. Trace element compositions of different soils from the fossil site were also analyzed by solution ICP-MS, employing progressive leaches that included distilled H₂O, 0.1 M acetic acid, and microwave digestion in concentrated HCl-HNO₃. In teeth, trace element uptake in enamel is 2-4 orders of magnitude slower than in dentine, forming an effective trace element barrier. Uptake in dentine parallel to the dentine-enamel interface is enhanced by at least 2 orders of magnitude compared to transverse, causing trace element “plumes” down the tooth core. In bone, U, Ba and Sr are nearly homogeneous, implying diffusivities ∼5 orders of magnitude faster than in enamel and virtually complete equilibration with host soils. In contrast all REE show strong depletions inward, with stepwise linear segments in log-normal or inverse complementary error function plots; these data require a multi-medium diffusion model, with about 2 orders of magnitude difference in slowest vs. fastest diffusivities. Differences in REE diffusivities in bone (slow) vs. dentine (fast) reflect different partition coefficients (K_d’s). Although acid leaches and bulk digestion of soils yield comparable fossil-soil K_d’s among different elements, natural solutions are expected to be neutral to slightly basic. Distilled H₂O leachates instead reveal radically different K_d’s in bone for REE than for U-Sr-Ba, suggest orders of magnitude lower effective diffusivities for REE, and readily explain steep vs. flat profiles for REE vs. U-Sr-Ba, respectively. Differences among REE K_d’s and diffusivities may explain inward changes in Ce anomalies. Acid washes and bulk soil compositions yield misleading K_d’s for many trace elements, especially the REE, and H₂O-leaches are preferred. Patterns of trace element distributions indicate diagenetic alteration at all scales, including enamel, and challenge the use of trace elements in paleodietary studies.     

贾湖史前人类迁移行为的初步研究——锶同位素分析技术在考古学中的运用

位于河南省舞阳县的贾湖遗址是一处著名的新石器时代遗址,距今7800～9000年。遗址中出土了大量的人和动物的骨骼与牙齿,这为研究史前时期中国中部地区人类的迁移情况提供了很好的材料。在本次研究中,共分析了26个人和动物样品,包括12个人体骨密质样品、9个人牙釉质样品和5个猪牙釉质样品。测定了每个样品的锶同位素浓度和87Sr/86Sr比值,结果表明猪牙釉质的锶同位素浓度（平均值为196±51ppm,n=5,1σ）高于人牙釉质的浓度（平均值为110±61ppm,n=9,1σ）,人骨骼的锶同位素浓度（平均值为444±173ppm,n=12,1σ）明显地高于人牙釉质的浓度。根据5个猪牙釉质样品87Sr/86Sr平均值±2倍的标准偏差确定的当地锶同位素比值范围（0.712205～0.712420）,发现14个人类个体中有5个是外来迁入的,并且从第1期到第3期人口的迁移率有增加的趋势。这是在国内首次利用锶位素分析方法对古人类的迁移现象进行研究,同时也表明此方法可以很好地判断古人类迁移行为。     

砂岩型铀矿微区原位U-Pb同位素定年技术方法研究

铀矿物定年一直是成矿年代学中的难点,随着微区原位U-Pb同位素定年技术的发展,可以直接针对矿石矿物(铀矿物)进行同位素定年;但是其中的砂岩型铀矿由于其存在状态复杂,在原位定年中剥蚀要求高,也缺乏合适的外部校正标准物质,所以定年准确度有待提高。本文研究了两种微区原位U-Pb同位素测年的方法,对砂岩型铀矿定年进行了尝试,试图解决铀矿测年中的无基体匹配问题并提高砂岩型铀矿定年水平。一是建立了一种激光剥蚀多接收电感耦合等离子体质谱仪联合电子探针进行微区原位U-Pb同位素测年的技术(LA-MC-ICP-MS&EMPA)。通过优化实验方法,对秦岭陈家庄花岗岩型铀矿进行了测试,获得与同位素稀释热电离质谱法(ID-TIMS)一致的年龄结果,证明了微区原位U-Pb同位素测年无基体匹配标准物质分析的可行性;并利用此法获得鄂尔多斯盆地红庆河和塔然高勒砂岩型铀矿的微区原位U-Pb同位素年龄信息。二是尝试了利用飞秒激光剥蚀多接收电感耦合等离子体质谱法(fsLA-MC-ICP-MS)对红庆河和宁夏宁东砂岩型铀矿样品进行微区原位U-Pb同位素定年,并获得了微区原位U-Pb同位素年龄,表明飞秒激光剥蚀技术在砂岩型铀矿定年中有很好的应用前景。本文提出,比较单一且年龄偏老的单矿物样品可以选择LA-MC-ICP-MS&EMPA联合法进行分析,需要高空间分辨率的样品建议使用fsLA-MC-ICP-MS法。