热电离质谱法测定龋齿牙釉质87Sr/86Sr同位素比值

锶同位素已经成为国际考古学界用于探索人和动物迁移活动和食谱组成的主要方法。本文利用锶特效树脂(Sr-Spec), 建立了快速分离富集于人龋齿中的微量元素锶, 并测定87Sr/86Sr的有效方法。采用硝酸-高氯酸体系消解龋齿样品, 利用锶特效树脂(Sr-Spec)快速分离富集龋齿中微量元素锶(Sr), 最后采用IsoProbe-T固体热电离质谱计测定龋齿87Sr/86Sr同位素比值。实验结果表明, 不同年龄和性别龋齿牙釉质的87Sr/86Sr同位素比值在0.710935~0.711034之间较小区间范围, 基本趋于稳定, 说明生活在相同地质背景的人或动物, 其机体内Sr同位素比值接近。男性龋齿牙釉质87Sr/86Sr比值随着年龄的增长有微小的波动, 从0.710935升高到0.711031, 这些微小变化可能与样本人群的环境和生活习惯相关。     

陶寺遗址中晚期出土部分人类牙釉质的锶同位素比值分析

陶寺遗址位于山西省襄汾县陶寺镇,距今4300~3900年。经过多次较大规模的发掘,陶寺遗址成为我国规模最大的、显现文明化程度最高的史前聚落遗址之一,也是研究中国史前至夏商时期城址都市化进程中的一个重要的里程碑式遗址。本文通过热电离质谱分析方法对陶寺遗址中晚期遗迹出土的21个个体人类牙釉质的锶同位素比值进行了测定。结果表明,这些人类牙釉质的锶同位素比值平均值是0.711374(2σ=0.000680,n=21)。与以前建立的遗址当地的锶同位素比值范围比较可知,有6个个体可能在遗址当地出生,由此推测本地个体占总数28.6%左右;还有15个个体牙釉质的锶同位素比值在遗址当地的锶同位素比值范围以外,表明这些个体可能在其他地区出生,推测外来者占总数的71.4%左右。由此可知,在陶寺文化中期至晚期的陶寺遗址的先民中,存在很高比例的外来移民。     

MC-ICP-MS高精度测定Li同位素分析方法

以不同浓度Li元素标准样品和K、Ca、Na、Mg、Fe单元素标准样品的混合溶液为研究对象,采用3根阳离子交换树脂（AG 50W X8,200~400目）填充的聚丙烯交换柱和石英交换柱对Li进行分离富集,淋洗液分别为28 mol/L HCl、015 mol/L HCl以及05 mol/L HCl 30%乙醇,淋洗液体积小,仅为38 mL。分离回收率高,均大于976%。国际标样AGV 2（相对于IRMM 016）、BHVO 2（相对于IRMM 016）和IRMM 016（相对于L SVEC）的δ7Li值分别为(513±094)‰(2σ,n=10)、(408±060)‰(2σ,n=4)和(0038±073)‰(2σ,n=10),与前人分析结果吻合,分析精度与国际同类实验室水平相当。并对比了马里兰大学同位素实验室和笔者实验室对同种岩石矿物样品的分析结果,在误差范围内具有很好的一致性。此外,对美国地质调查局提供的准标样NKT 1霞石岩（相对于IRMM 016）给出了定值,δ7Li值为(871±046)‰(2σ,n=4)。因此,本方法可用于测定天然样品的Li同位素组成。     

大贵州滩二叠系—三叠系界线附近锶同位素组成特征

位于贵州南部的“大贵州滩”上,二叠系—三叠系界线附近地层为一套连续的发育完整的碳酸盐岩。二叠系顶部主要为厚层生物屑泥粒灰岩,而三叠系底部则主要为钙质微生物骨架灰岩及厚层粒泥灰岩。穿过二叠系—三叠系界线的取样累计厚度81m,二叠系和三叠系大致各占一半的厚度,共取样品91件,n(87Sr)/n(86Sr)值变化在0.707269～0.707409之间,平均为0.707327,低于现代海水的锶同位素比值的平均值（0.7090737）。锶同位素比值变化曲线表明从晚二叠世末期到早三叠世初期,同位素比值虽小幅度的起伏波动频繁,但总体上没有明显变化,三叠系底部的平均值（0.707330）略高于二叠系顶部的平均值（0.707323）。大贵州滩晚二叠世末至早三叠世初锶同位素组成的总体演化趋势与扬子台地及世界其它地方同时期的锶同位素组成的演化趋势（呈急剧的上升）不同,造成这种状况的原因可能是在全球事件控制的大背景下,由于大贵州滩特殊的环境条件,陆源物质对其影响小,导致了壳源锶对锶同位素组成的制约作用减弱,因而锶同位素组成未发生明显变化。     

云南思茅盆地钾盐矿床的深源浅储成因模式——来自于Sr同位素的证据

【研究目的】思茅盆地赋存有中国唯一的前第四纪固体钾盐矿床,该矿床的成因一直存在争议。客观地认识矿床成因、合理地构建矿床成因模式,不仅是钾盐矿床学研究中亟需解决的基础科学问题,而且关乎盆地内钾盐资源勘查方向的选择。【研究方法】本项研究以思茅盆地L-2井和MZK-3井的盐岩、盐岩上覆和下伏碎屑岩、盐岩中的碎屑岩为主要研究对象,重点分析其锶同位素地球化学特征。【研究结果】结果表明：（1）L-2井全岩样品⁸⁷Sr/⁸⁶Sr值为0.708220~0.727458,平均值为0.712776;盐岩水不溶物⁸⁷Sr/⁸⁶Sr值为0.711342~0.741999,平均值为0.716574;（2）MZK-3井盐岩上覆碎屑岩层⁸⁷Sr/⁸⁶Sr值为0.713318~0.723147,平均值为0.717255;盐岩下伏碎屑岩层⁸⁷Sr/⁸⁶Sr值为0.712470~0.738988,平均值为0.719307;（3）碎屑岩样品经过87Rb校正恢复至初始沉积状态的⁸⁷Sr/⁸⁶Sr值为0.710880~0.727678,平均值为0.712828;（4）盐岩样品⁸⁷Sr/⁸⁶Sr值全部明显小于大陆地表风化系统的平均值,有个别样品⁸⁷Sr/⁸⁶Sr值大于现代海水。【结论】基于思茅盆地基础地质和钾盐矿床地质已有的研究成果,结合盐岩和碎屑岩锶同位素地球化学特征,可以得出：思茅盆地含钾盐岩与碎屑岩处于不同的锶同位素平衡体系;含钾盐岩的物源主体为海水,成盐过程中陆源淡水的补给可使⁸⁷Sr/⁸⁶Sr值增大;碎屑岩沉积于陆相环境,在与固态盐岩或盐岩水溶液接触之前已处于早成岩阶段A亚期;钾盐的成矿模式为勐野井组沉积期深层源盐通过走滑拉分形成的断层迁移至地表,在由高处向汇水盆地迁移过程中捕获了处于早成岩阶段A亚期的碎屑颗粒,形成了现今的含泥砾盐岩;部分含泥砾盐岩在迁移进入汇水盆地之后,经历了溶解-重结晶的过程,形成了盆地内成分较纯的盐岩;后续沉积的碎屑颗粒形成了防止盐岩溶蚀破坏的保护层;新生代的喜山运动使早期形成的钾盐矿床发生调整改造。     

南秦岭大巴山大型钡成矿带中锶同位素组成及其成因意义

为探讨南秦岭大巴山大型钡成矿带中毒重石矿床与重晶石矿床的差异性,文中对大型钡成矿带的锶同位素组成特点进行了研究。结果表明,寒武系地层钡矿床中23件钡解石、毒重石、重晶石样品的87Sr/86Sr比值集中在0.707 771~0.708 869,平均值为0.708 379,低于寒武纪海水87Sr/86Sr比值(0.709),反映了成矿流体中有幔源物质的混入,锶同位素组成可能是海水与海底热卤水混合的结果,该过程类似于造成重晶石在海底沉积物中富集的现代洋底热水活动。志留系地层钡矿床中12件钡解石、毒重石、重晶石样品87Sr/86Sr比值集中在0.708 242~0.708 809,平均值为0.708 447,高于志留纪海水87Sr/86Sr比值(0.707 93),可能是同时代海水与深部热水混合所致,并有较高放射性成因壳源锶的混染。锶同位素组成可能是海水与海底热卤水混合的结果。文中锶同位素的研究为南秦岭大巴山大型钡成矿带的海底热水沉积成因提供了新的证据。     

云南含罗平生物群层位锶同位素组成与演化

现有公布的数据显示,海水87Sr/86Sr值在中三叠世安尼期较为平稳,有别于早三叠世因环境导致的动荡变化,为二叠纪末生物大灭绝之后生物复苏的加速期,而罗平生物群就是该加速期的标志性生物群。本文研究了含罗平生物群层位标准剖面-大凹子剖面上连续沉积的26件碳酸盐岩样品的锶同位素组成与演化,用于了解含罗平生物群层位沉积海水锶同位素的变化趋势。结果显示:(1)碳酸盐岩中Sr平均值大于2000×10-6,主要来自于文石和海洋成岩作用;(2)低Mn和Mn/Sr0.4说明:87Sr/86Sr数据在很大程度上能代表同时期海水中的87Sr/86Sr比值;(3)这些样品的87Sr/86Sr值变化在0.707969～0.708253,平均值为0.708025,锶同位素比值变化曲线呈小幅度的起伏波动,其值明显大于同时期欧洲等地公布的数据,但同华南其他地区公布的数据具有相似性,推测含罗平生物群层位锶同位素组成仅代表区域事件,受印支运动影响。     

大别山麻粒岩和TTG片麻岩的Sr,Nd,Pb同位素地球化学

北大别4个麻粒岩和4个TTG片麻岩样品的Sr,Nd同位素分析结果表明，样品普遍具有较高的锶同位素比值（^87Sr/^86Sr=0.7066-0.7461)，较低的Nd同位素比值（^143Nd/^144Nd=0.5108-0.5124)，表现出明显的壳源特征，结合铅同位素的组成来看，北大别麻粒岩及TTG片麻岩的同位素成分相当于－下地壳。岩石的特源为古老的地壳，大约在2－3Ga之间，少数样品的同位素特征可能暗示源区有年轻地壳物质的加入。     

山西省襄汾县陶寺遗址出土动物牙釉质的锶同位素比值分析

锶同位素分析技术已经成为国际考古学界用于探索人和动物迁移活动的主要方法.陶寺遗址位于山西省襄汾县陶寺镇,距今4500～3900年,是目前我国规模最大的、显现文明化程度最高的史前聚落遗址之一.文章通过热电离质谱分析方法对山西襄汾县陶寺镇陶寺遗址龙山晚期出土动物的14个动物牙釉质的锶同位素比值进行了测定.研究结果表明,5个...     

锶同位素地层学研究进展

锶同位素地层学（SIS）根据地质历史中的任何时间全球范围内海水的 锶同位素组成都是均一的，海水87Sr/86Sr比值随时间变化这一基本原理，利用代表原始海水的海相碳酸盐（以及磷酸盐和硫酸盐）的87Sr/86Sr比值确定海相地层的年代，研究海平面变化，造山运动，古气候等全球事件，在地层学，沉积学，石油地质学和矿床学等领域中有着广泛的应用前景，同位素地层学已在世界范围内得到地质学家的普遍关注，并已获得迅速的发展，国内的有关研究则刚刚起步，锶同位素地层学研究的难点主要在于对样品成岩蚀变的挖掘和分析技术上，同时还需要有良好的地层学研究基础，在样品选择上应充分考虑其原始组分的抗成岩蚀变能力，锶同位素地层学的研究需要地层学家，沉积学家和地球化学家的共同努力。     

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.     

Mobility and exile at 2nd century A.D. khirbet edh‐dharih: Strontium isotope analysis of human migration in western Jordan

The 2nd century A.D. Roman annexation of the Nabataean Kingdom may have resulted in significant settlement disruption. Here we investigate the possibility that political refugees occupied Khirbet edh‐Dharih after Roman takeover, using strontium isotope analysis of archaeological human dental enamel. We additionally discuss regional patterning of 87Sr/86Sr in western Jordan based on archaeological faunal dental enamel samples to understand strontium isotope spatial heterogeneity and to facilitate interpretation of the Dharih results. Strontium isotope analysis of small mammal dentition varied as expected based on bedrock geology, but small faunal sample sizes did not accurately reflect the broad range of biologically available strontium at Dharih. Only one person at Khirbet edh‐Dharh appears to be non‐local based on isotopic data. The status of the remaining individuals is unclear, as they could have originated from Dharih or the Nabataean capital city of Petra. Incorporating modern fauna and soil samples to establish the local value may assist in characterizing the local strontium in a geologically complex area such as Dharih. Futhermore, future analysis of elemental strontium to assess dietary composition and diagenetic contamination would facilitate interpretation of the strontium sources in the Dharih individuals. © 2008 Wiley Periodicals, Inc.     

Determination of Sr isotopes in calcium phosphates using laser ablation inductively coupled plasma mass spectrometry and their application to archaeological tooth enamel

The determination of accurate Sr isotope ratios in calcium phosphate matrices by laser ablation multi-collector ICP-MS is demonstrated as possible even with low Sr concentration archaeological material. Multiple on-line interference correction routines for doubly-charged REE, Ca dimers and Rb with additional calibration against TIMS-characterised materials are required to achieve this. The calibration strategy proposed uses both inorganic and biogenic apatite matrices to monitor and correct for a ⁴⁰Ca-³¹P-¹⁶O polyatomic present at levels of 0.3-1% of the non-oxide peak, which interferes on ⁸⁷Sr causing inaccuracies of 0.03-0.4% in the ⁸⁷Sr/⁸⁶Sr isotope ratio. The possibility also exists for synthetic materials to be used in this calibration. After correction for interferences total combined uncertainties of 0.04-0.15% (2SD) are achieved for analyses of 13-24 μg of archaeological tooth enamel with Sr concentrations of ca. 100-500 ppm using MC-ICP-MS. In particular, for samples containing >300 ppm Sr, total uncertainties of ∼0.05% are possible utilising 7-12 ng Sr. Data quality is monitored by determination of ⁸⁴Sr/⁸⁶Sr ratios.When applied to an archaeological cattle tooth this approach shows Sr-isotope variations along the length of the tooth in agreement with independent TIMS data. The ⁴⁰Ca-³¹P-¹⁶O polyatomic interference is the root cause of the bias at mass 87 during laser ablation ICP-MS analysis of inorganic and biogenic calcium phosphate (apatite) matrices. This results in inaccurate ⁸⁷Sr/⁸⁶Sr ratios even after correction of Ca dimers and doubly charged rare earth elements. This interference is essentially constant at specific ablation conditions and therefore the effect on ⁸⁷Sr/⁸⁶Sr data varies in proportion to changes in the Sr concentration of the ablated material. Complete elimination of this interference is unlikely through normal analytical mechanisms and therefore represents a limitation on the achievable accuracy of LA-(MC-)ICP-MS ⁸⁷Sr/⁸⁶Sr data without rigorous calibration to known reference materials.     

中国古代家养动物的动物考古学研究

鉴定家养动物的系列方法包括形体测量、病理现象、年龄结构、性别特征、数量比例、考古现象、食性分析、DNA研究等。按照迄今为止出土的动物骨骼资料,中国主要家养动物开始出现的时间和种类依次为距今10000年左右出现狗,距今9000年左右出现猪,距今5000多年出现绵羊,距今4000多年出现黄牛,距今约3700年左右出现马和山羊,距今约3600年左右出现鸡。中国古代家养动物出现的模式可以分为直接在当地驯化和通过文化交流从其他地区引进这样两种。     

Reconstructing the migration patterns of late Pleistocene mammals from northern Florida, USA

We used analyses of the strontium isotope (⁸⁷Sr/⁸⁶Sr) ratios of tooth enamel to reconstruct the migration patterns of fossil mammals collected along the Aucilla River in northern Florida. Specimens date to the late-glacial period and before the last glacial maximum (pre-LGM). Deer and tapir displayed low ⁸⁷Sr/⁸⁶Sr ratios that were similar to the ratios of Florida environments, which suggest that these taxa did not migrate long distance outside of the Florida region. Mastodons, mammoths, and equids all displayed a wide range of ⁸⁷Sr/⁸⁶Sr ratios. Some individuals in each taxon displayed low ⁸⁷Sr/⁸⁶Sr ratios that suggest they ranged locally, while other animals had high ⁸⁷Sr/⁸⁶Sr ratios that suggest they migrated long distances (> 150 km) outside of the Florida region. Mastodons were the only taxa from this region that provided enough well-dated specimens to compare changes in migration patterns over time. Pre-LGM mastodons displayed significantly lower ⁸⁷Sr/⁸⁶Sr ratios than late-glacial mastodons, which suggests that late-glacial mastodons from Florida migrated longer distances than their earlier counterparts. This change in movement patterns reflects temporal changes in regional vegetation patterns.     

Anglo-Saxon animal husbandry techniques revealed though isotope and chemical variations in cattle teeth

The Sr concentration and isotope composition of tooth enamel from domesticated animals from two neighbouring Anglo-Saxon settlements, at Empingham (6–7th century) and Ketton (10–12th century) in Rutland, central England, are compared both with each other, and with associated human populations. Data from the Empingham II site form discrete fields in Sr concentration and isotope composition space for cattle, pig and sheep with a partial overlap of the human and pig fields. By contrast there is significant overlap in all the animal and human data fields from the Ketton site. The differences in data distribution between the two sites are attributed to animal husbandry techniques, as the surface geology of the two areas is very similar, implying geological factors are an unlikely cause of the difference. It is suggested that the grazing and feeding patterns of animals at the Empingham II site were controlled and restricted, whereas at the Ketton site the animals grazed and foraged freely over a common area.     

Strontium and hydrogen isotope geochemistry of fresh and metabasalt dredged from the Mid-Atlantic Ridge

Fresh basalt and metabasalt dredged from the Mid-Atlantic Ridge were studied for Na, K, Rb, Sr, and H₂O(+) contents, and strontium and hydrogen isotope ratios. Na, K, Rb, and Sr contents of these samples are within the range of those of oceanic tholeiite. H₂O(+) content, strontium, and hydrogen isotope ratios vary widely. The variation in water content of metabasalt is apparently related to the chlorite content. The metamorphic temperature was about 550 °C based on the estimated δD value of chlorite. There is positive linear relationship between water content and strontium isotope ratio. Based on this relationship, the variation of strontium isotope ratio of the metabasalt was interpreted as follows: complete exchange occurred between strontium in the chlorite portion of the metabasalt and strontium in sea water (⁸⁷Sr/⁸⁶Sr ratio=0.7090), while the original strontium (⁸⁷Sr/⁸⁶Sr∼0.7023) was retained in the non-altered portion of the basalts.     

西藏南部晚白垩世厚壳蛤的锶同位素年龄标定

沉积岩样品年龄的直接标定是沉积学与地层学研究的难点之一.由于锶在海水中的残留时间(≈106a) 大大长于海水的混合时间(≈103a), 因而同一时间全球海水的锶元素在同位素组成上是均一的, 并造成地质历史中海水的锶同位素组成是时间的函数, 这是锶同位素地层学(SIS) 的基本原理和利用锶同位素地层学进行海相地层定年的理论基础.本文根据锶同位素地层学的基本原理, 测试了西藏南部岗巴剖面上白垩统宗山组上段地层中厚壳蛤化石的锶同位素组成, 尝试对这些化石进行了年龄标定, 4个样品分别位于剖面累计厚度381, 362, 358和296m处, 其87Sr/86Sr比值分别为0.707832, 0.707769, 0.707768和0.707695, 年龄的标定结果分别是65.68, 69.34, 69.39和72.32Ma, 定年的平均误差为±1Ma左右.研究结果表明, 锶同位素地层学在海相地层定年方面具有潜在价值.      

重庆秀山寒武系锶同位素演化曲线及全球对比

本文评述了国际上已有的寒武纪海相碳酸盐的锶同位素演化曲线，公布了重庆秀山寒武系海相碳酸盐的锶同位素分析结果，尽管对样品进行了成岩蚀变检测和必要的筛选，但样品仍可能不同程度地经历了成岩蚀变，锶同位素组成与地层厚度投点图显得较为离散，笔者主要利用87Sr/86Sr比值较低的样品建立的寒武纪海水的锶同位素演化曲线在长期旋回上与国际上已公布的同时代锶同位素演化曲线仍具有较好相似性和可比性，说明全球事件是海水锶同位素组成的主要控制因素，海水的87Sr/86Sr比值在盆内对比，盆间对比，以及全球对比中都具有潜在价值。根据锶同位素地层学的基本原理，笔者尝试确定了重庆秀山寒武纪剖面一些关键点的年龄，累积厚度1340m处的年龄为503－509Ma，累积厚度1950m处的年龄为496－498Ma，这对秀山寒武纪剖面下，中寒武统和中、上寒武统界线的确定具有参考价值。