激光剥蚀原位铀系法对化石年龄的测定

doi:10.16359/j.1000-3193/AAS.2024.0072

摘要/Abstract

摘要： 哺乳动物的骨骼和牙齿化石常见于考古和古人类遗址且铀含量较高，可用于铀系直接测年，但难题在于，化石是开放体系，不满足放射性同位素测年关于样品保持“封闭体系”的假设前提。为了获取化石内部铀浓度和铀钍同位素的空间分布数据，以解译铀吸附模式和铀系衰变不平衡的年代信息，本文发展了激光剥蚀原位分析铀钍同位素的方法，并详细描述了标准样品制备、仪器调谐、激光剥蚀、同位素测试和数据处理的相关流程。此外，本文利用激光剥蚀原位分析技术分析了许家窑人遗址的两颗马牙化石。结果表明出自上文化层的样品XJY-1929经历了铀早期吸附，其扩散模型的铀系年代为172.0±5.1 kaBP；而下文化层的样品XJY-3055经历了相对晚期吸附，其扩散模型的铀系年代为58.8±4.5 kaBP，显著小于地层的地质年代，这可能是由于该样品长期处于还原环境造成的结果。

关键词: 骨骼化石, 牙齿化石, 激光剥蚀, 铀系原位定年, 许家窑人遗址

Abstract:

U-series dating of fossil bones and teeth is based on the fact that U is incorporated into the fossils during their burial and subsequently decays to the daughter nuclides towards equilibrium. However, it has been long-known that the diagenetic phenomenon of uranium uptake influences the reliability of U-series dating of fossils. Over the past two decades, significant advances have been made in the technology of U and Th isotopic analyses. Today, it is able to achieve ɛ-precision of U-Th isotopic ratios using the state of art of Multi-Collector Inductively Coupled Plasma Mass Spectrometer (MC-ICPMS) and to achieve micrometer scale of spatial resolution with Laser Ablation-ICPMS (but with lower precision). It seems most timely to further develop U-series dating method for fossils using the high-precision and high-resolution analytical techniques. We therefore developed a LA-MC-ICPMS method for U-series in situ dating of fossil samples from Paleolithic and/or paleoanthropological sites. We described the details of our method, including standard preparation, LA-MC-ICPMS calibration, laser ablation, U-Th isotopic measurements and data treatment. Using the newly established method, we analyzed two mammalian fossil teeth from the Xujiayao hominin site, in Nihewan Basin. The sample XJY-1929, from the Upper Culture Layer, displayed U-shaped distribution of U-content, ²³⁴U/²³⁸U and ²³⁰Th/²³⁸U activity ratios, indicating an early uptake process, and yielded a DAD model age of 172.0±5.1 kaBP, representing a minimum age of this fossil. The sample XJY-3055, from the Lower Culture Layer, however, showed apparently lower U-content, ²³⁴U/²³⁸U and ²³⁰Th/²³⁸U activity ratios, with a DAD model age of 58.8±4.5 kaBP, which is much younger than the geologic age of the layer. This sample probably experienced a later U-uptake, caused by the redox conditions in the Lower Culture Layer.

Key words: fossil bones, fossil teeth, laser ablation, U-series in situ dating, Xujiayao hominin site

中图分类号:

P533

刘玥, 焦亚诺, 卢泽基, 胡贵兰, 邵庆丰. 激光剥蚀原位铀系法对化石年龄的测定[J]. 人类学学报, 2025, 44(04): 700-714.

LIU Yue, JIAO Yanuo, LU Zeji, HU Guilan, SHAO Qingfeng. U-series in situ dating of fossils by LA-MC-ICPMS[J]. Acta Anthropologica Sinica, 2025, 44(04): 700-714.

图/表 7

图1 LA系统与MC-ICPMS联用结构示意图激光剥蚀系统(Laser Ablation system, LA）由激光发生器、光束传输系统、样品剥蚀池和观测系统组成：激光发生器用于产生高能激光，通过一系列透镜、反射镜构成的光路传输系统反射激光至聚焦物镜上对固体样品表面进行剥蚀，剥蚀融化得到的物质冷凝为气溶胶粒子，通过气路传输系统辅以高纯度氦气和氩气的混合气体将样品池中的气溶胶颗粒吹扫，经信号匀化器运输到ICP中。在到达等离子体火焰之前，加入少量氮气以提高信号灵敏度。气溶胶经高温等离子体火焰(~6000 K）分解和电离产生离子束，随后被提取到质谱仪中进行同位素组成分析。A laser ablation system, LA, consists of a laser source, laser beam path, sample pool, and sample observation system. The laser source is used to produce a laser of sufficient power. The output laser beam, is adjusted through a series of mirrors and/or prisms, to focus onto the sample surface to ablate sample. The sample aerosols generated by the laser ablation process are transported to the ICP by a mixture of Ar and He gases, and before reaching the plasma flame, a small quantity of N2 gas is added to enhance the sensitivity. The aerosols are dissociated and ionized by the high temperature of the plasma flame (~6000 K) to produce an ion beam, which is subsequently extracted for isotope analysis using a mass spectrometer.

Fig.1 Structure diagram of LA system combined with MC-ICPMS

图2 许家窑人遗址的马牙化石样品XJY-1929和XJY-3055 矩形框表示用于LA-MC-ICPMS分析的区域，红色线段代表扫描路径，红色圈点代表激光剥蚀点。The rectangles indicate the area for LA-MC-ICPMS analyses, where the red lines represent the LA scan tracks, and the red circles are the LA spots.

Fig.2 Fossil teeth XJY-1929 and XJY-3055 from Xujiayao hominin site

图3 XJY-1929牙本质的LA-MC-ICPMS铀系分析和DAD模拟 a.蓝线分别表示线扫描的238U信号强度(V），234U/238U原子比，230Th/238U原子比；红点代表点分析的铀含量(μg/g），234U/238U活度比，230Th/238U活度比；黑点为表观铀系年代。Blue curves represent, respectively, the 238U ion beam intensity (V), the 234U/238U and 230Th/238U atomic ratios, measured by raster scan; red points represent, respectively, the U-concentration (μg/g), 234U/238U and 230Th/238U activity ratios; black points are the apparent U-series ages; b.图上点为234U/238U和230Th/238U活度比的测量值，弧线为DAD模拟结果。Data points are the measured values of 234U/238U and 230Th/238U activity ratios and the curves are the results of DAD modeling.

Fig.3 LA-MC-ICPMS U-series analysis and DAD modeling of the sample XJY-1929 dentin

表1 许家窑人遗址的马牙化石LA-MC-ICPMS铀系原位测年结果

Tab.1 LA-MC-ICPMS U-series in situ dating results for the fossil teeth from Xujiayao hominin site

标本编号Sample ID	w(U) (μg/g)	²³⁴U/²³⁸U	²³⁰Th/²³⁸U	²³⁰Th/²³²Th	年代Age (kaBP)	(²³⁴U/²³⁸U)_i
XJY1929-1	245.3±74.1	1.312±0.007	0.940±0.009	>1000	127.5±2.5	1.447±0.011
XJY1929-2	230.4±69.7	1.330±0.007	1.038±0.012	>1000	149.4±3.8	1.503±0.012
XJY1929-3	222.3±67.3	1.315±0.007	1.033±0.011	>1000	151.6±3.8	1.483±0.012
XJY1929-4	227.2±68.9	1.317±0.007	1.044±0.009	>1000	154.6±3.4	1.490±0.012
XJY1929-5	228.4±69.3	1.309±0.007	1.004±0.009	>1000	144.9±3.1	1.466±0.011
XJY1929-6	215.5±65.3	1.305±0.007	1.008±0.009	>1000	147.1±3.1	1.462±0.011
XJY1929-7	241.3±73.3	1.301±0.007	1.014±0.009	>1000	149.8±3.1	1.459±0.011
XJY1929-8	210.2±63.8	1.299±0.007	1.009±0.009	>1000	149.1±3.2	1.455±0.011
XJY1929-9	219.6±66.6	1.301±0.007	1.006±0.008	>1000	147.7±2.9	1.456±0.011
XJY1929-10	210.8±64.0	1.302±0.007	1.015±0.008	>1000	149.8±3.1	1.461±0.012
XJY1929-11	204.7±62.2	1.305±0.007	1.017±0.009	>1000	149.8±3.2	1.465±0.012
XJY1929-12	219.9±67.8	1.302±0.011	1.009±0.008	>1000	148.1±3.6	1.459±0.017
XJY1929-13	218.7±66.3	1.321±0.007	1.002±0.008	>1000	141.5±2.8	1.478±0.011
XJY1929-14	215.1±65.5	1.319±0.007	0.997±0.008	>1000	140.6±2.8	1.474±0.011
XJY1929-15	206.0±62.6	1.334±0.007	1.069±0.010	>1000	157.5±3.6	1.521±0.013
XJY1929-16	196.6±59.7	1.332±0.007	1.039±0.009	>1000	149.2±3.1	1.505±0.012
XJY1929-17	210.6±63.8	1.314±0.006	0.978±0.011	>1000	136.6±3.2	1.462±0.010
XJY1929-18	153.1±46.4	1.332±0.008	1.013±0.010	>1000	141.9±3.1	1.496±0.012
XJY1929-19	176.1±53.3	1.324±0.006	1.013±0.011	>1000	143.7±3.3	1.486±0.011
XJY1929-20	230.3±69.9	1.308±0.006	1.023±0.011	>1000	150.7±3.6	1.471±0.011
XJY1929-21	230.5±69.8	1.307±0.006	1.029±0.011	>1000	152.7±3.7	1.472±0.011
XJY1929-22	241.6±73.1	1.302±0.006	1.034±0.011	>1000	155.6±3.8	1.469±0.011
XJY1929-23	252.1±76.3	1.301±0.006	1.021±0.011	>1000	152.0±3.7	1.462±0.011
XJY1929-24	252.6±76.5	1.302±0.006	1.021±0.012	>1000	151.7±3.8	1.463±0.011
XJY1929-25	186.0±56.1	1.312±0.006	0.989±0.010	>1000	140.3±3.1	1.463±0.010
XJY1929-26	243.7±74.2	1.273±0.007	1.007±0.009	>1000	155.3±3.6	1.424±0.012
XJY1929-27	190.1±57.6	1.327±0.007	0.993±0.009	>1000	137.8±2.8	1.482±0.012
XJY1929-28	209.5±63.2	1.314±0.006	1.051±0.015	>1000	157.5±5.0	1.490±0.012
XJY3055-1	4.1±1.2	1.158±0.008	0.516±0.007	328	63.2±1.4	1.189±0.009
XJY3055-2	2.0±0.6	1.138±0.011	0.488±0.012	645	60.1±2.1	1.163±0.013
XJY3055-3	2.3±0.7	1.137±0.009	0.370±0.009	666	42.5±1.4	1.154±0.010
XJY3055-4	1.7±0.5	1.147±0.010	0.368±0.012	772	41.7±1.7	1.165±0.011
XJY3055-5	3.0±0.9	1.143±0.008	0.347±0.008	789	39.1±1.2	1.160±0.009
XJY3055-6	2.0±0.6	1.140±0.009	0.420±0.011	898	49.5±1.6	1.162±0.010
XJY3055-7	1.3±0.4	1.152±0.012	0.404±0.010	653	46.5±1.5	1.173±0.013
XJY3055-8	13.1±3.9	1.154±0.006	0.425±0.007	222	49.5±1.0	1.177±0.007

表1 许家窑人遗址的马牙化石LA-MC-ICPMS铀系原位测年结果

Tab.1 LA-MC-ICPMS U-series in situ dating results for the fossil teeth from Xujiayao hominin site

标本编号Sample ID	w(U) (μg/g)	²³⁴U/²³⁸U	²³⁰Th/²³⁸U	²³⁰Th/²³²Th	年代Age (kaBP)	(²³⁴U/²³⁸U)_i
XJY1929-1	245.3±74.1	1.312±0.007	0.940±0.009	>1000	127.5±2.5	1.447±0.011
XJY1929-2	230.4±69.7	1.330±0.007	1.038±0.012	>1000	149.4±3.8	1.503±0.012
XJY1929-3	222.3±67.3	1.315±0.007	1.033±0.011	>1000	151.6±3.8	1.483±0.012
XJY1929-4	227.2±68.9	1.317±0.007	1.044±0.009	>1000	154.6±3.4	1.490±0.012
XJY1929-5	228.4±69.3	1.309±0.007	1.004±0.009	>1000	144.9±3.1	1.466±0.011
XJY1929-6	215.5±65.3	1.305±0.007	1.008±0.009	>1000	147.1±3.1	1.462±0.011
XJY1929-7	241.3±73.3	1.301±0.007	1.014±0.009	>1000	149.8±3.1	1.459±0.011
XJY1929-8	210.2±63.8	1.299±0.007	1.009±0.009	>1000	149.1±3.2	1.455±0.011
XJY1929-9	219.6±66.6	1.301±0.007	1.006±0.008	>1000	147.7±2.9	1.456±0.011
XJY1929-10	210.8±64.0	1.302±0.007	1.015±0.008	>1000	149.8±3.1	1.461±0.012
XJY1929-11	204.7±62.2	1.305±0.007	1.017±0.009	>1000	149.8±3.2	1.465±0.012
XJY1929-12	219.9±67.8	1.302±0.011	1.009±0.008	>1000	148.1±3.6	1.459±0.017
XJY1929-13	218.7±66.3	1.321±0.007	1.002±0.008	>1000	141.5±2.8	1.478±0.011
XJY1929-14	215.1±65.5	1.319±0.007	0.997±0.008	>1000	140.6±2.8	1.474±0.011
XJY1929-15	206.0±62.6	1.334±0.007	1.069±0.010	>1000	157.5±3.6	1.521±0.013
XJY1929-16	196.6±59.7	1.332±0.007	1.039±0.009	>1000	149.2±3.1	1.505±0.012
XJY1929-17	210.6±63.8	1.314±0.006	0.978±0.011	>1000	136.6±3.2	1.462±0.010
XJY1929-18	153.1±46.4	1.332±0.008	1.013±0.010	>1000	141.9±3.1	1.496±0.012
XJY1929-19	176.1±53.3	1.324±0.006	1.013±0.011	>1000	143.7±3.3	1.486±0.011
XJY1929-20	230.3±69.9	1.308±0.006	1.023±0.011	>1000	150.7±3.6	1.471±0.011
XJY1929-21	230.5±69.8	1.307±0.006	1.029±0.011	>1000	152.7±3.7	1.472±0.011
XJY1929-22	241.6±73.1	1.302±0.006	1.034±0.011	>1000	155.6±3.8	1.469±0.011
XJY1929-23	252.1±76.3	1.301±0.006	1.021±0.011	>1000	152.0±3.7	1.462±0.011
XJY1929-24	252.6±76.5	1.302±0.006	1.021±0.012	>1000	151.7±3.8	1.463±0.011
XJY1929-25	186.0±56.1	1.312±0.006	0.989±0.010	>1000	140.3±3.1	1.463±0.010
XJY1929-26	243.7±74.2	1.273±0.007	1.007±0.009	>1000	155.3±3.6	1.424±0.012
XJY1929-27	190.1±57.6	1.327±0.007	0.993±0.009	>1000	137.8±2.8	1.482±0.012
XJY1929-28	209.5±63.2	1.314±0.006	1.051±0.015	>1000	157.5±5.0	1.490±0.012
XJY3055-1	4.1±1.2	1.158±0.008	0.516±0.007	328	63.2±1.4	1.189±0.009
XJY3055-2	2.0±0.6	1.138±0.011	0.488±0.012	645	60.1±2.1	1.163±0.013
XJY3055-3	2.3±0.7	1.137±0.009	0.370±0.009	666	42.5±1.4	1.154±0.010
XJY3055-4	1.7±0.5	1.147±0.010	0.368±0.012	772	41.7±1.7	1.165±0.011
XJY3055-5	3.0±0.9	1.143±0.008	0.347±0.008	789	39.1±1.2	1.160±0.009
XJY3055-6	2.0±0.6	1.140±0.009	0.420±0.011	898	49.5±1.6	1.162±0.010
XJY3055-7	1.3±0.4	1.152±0.012	0.404±0.010	653	46.5±1.5	1.173±0.013
XJY3055-8	13.1±3.9	1.154±0.006	0.425±0.007	222	49.5±1.0	1.177±0.007

图4 XJY-1929牙骨质的LA-MC-ICPMS铀系分析蓝线分别表示线扫描的238U信号强度(V），234U/238U原子比，230Th/238U原子比；红点代表点分析的铀含量(μg/g），234U/238U活度比，230Th/238U活度比；黑点为表观铀系年代(ka）。Blue curves represent, respectively, the 238U ion beam intensity (V), the 234U/238U and 230Th/238U atomic ratios, measured by raster scan; red points represent, respectively, the U-concentration (μg/g), 234U/238U and 230Th/238U activity ratios; black points are the apparent U-series ages.

Fig.4 LA-MC-ICPMS U- series analysis of the sample XJY-1929 cement

图5 XJY-1929牙骨质-珐琅质-牙本质的LA-MC-ICPMS铀系分析蓝线表示线扫描的238U信号强度(V）Blue curves represent the 238U ion beam intensity (V)；红点为表观铀系年代(ka) red points are the apparent U-series ages

Fig.5 LA-MC-ICPMS U-series analysis of XJY-1929 cementum-enamel-dentin

图6 XJY-3055牙本质的LA-MC-ICPMS铀系分析和DAD模拟 a.蓝线分别表示线扫描的238U信号强度(V）和234U/238U原子比；红点代表点分析的铀含量(μg/g），234U/238U活度比，230Th/238U活度比；黑点为表观铀系年代(ka）Blue curves represent, respectively, the 238U ion beam intensity (V), the 234U/238U atomic ratios, measured by raster scan; red points represent, respectively, the U-concentration (μg/g), 234U/238U and 230Th/238U activity ratios; black points are the apparent U-series ages。b.图上点为234U/238U和230Th/238U活度比的测量值，弧线为DAD模拟结果Data points are the measured values of 234U/238U and 230Th/238U activity ratios and the curves are the results of DAD modeling.

Fig.6 LA-MC-ICPMS U-series analysis and DAD modeling of the sample XJY-3055 dentin

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