Lead in prehistoric,historic and contemporary Japanese: stable isotopic study by ICP mass spectrometry

Lead concentration and isotopic composition of prehistoric (middle and latest Jomon era, 2000–4500 BP, n=6), historic (Edo era, 130–400 BP, n=10), and contemporary (died in 1987–88, n=15) Japanese bones, and deciduous teeth from contemporary Japanese children born during 1985–88 (n=17) were analyzed by inductively coupled plasma mass spectrometry. Lead concentration was lowest in Jomon bones and was higher in rural Edo, contemporary, and urban Edo, in that order. Elevated Pb concentration in historic Edo people, as reported previously, was reconfirmed. The average isotopic ratios (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb) in excavated (prehistoric and historic) bones, contemporary bones, and deciduous teeth were different from each other. The contemporary bones had the least radiogenic composition (mean ²⁰⁷Pb/²⁰⁶Pb: 0.879; mean ²⁰⁸Pb/²⁰⁶Pb: 2.126) while the excavated bones the most (0.848; 2.098), and teeth intermediate (0.866; 2.111). The comparison with the literature data of isotopic compositions of environmental samples showed that the isotopic composition of the excavated bones was within the range of Japanese ores, rocks and soils, indicating the absence of foreign Pb sources in preindustrialized Japan. That of the contemporary bones was closer to the average gasoline Pb, the use of which had been banned in the late 1970s, than to the Pb in airborne particulate matter or refuse incineration ash of 1980s. The average Pb isotopic ratios in the deciduous teeth was close to the isotopic ratios of Pb in airborne particulate matter and refuse incineration ash. These data indicated that the contemporary Japanese population was exposed to foreign Pb which had different isotopic composition from domestic Pb. Exposure to Pb of foreign origin was particularly evidently recorded in people born before the leaded gasoline ban. The history of human Pb contamination in Japan is discussed based on the present results and other previously published data.     

ICP-MS测定生物样品中的微量金属元素

采用SP-60型恒压消解罐消解生物样品,用ICP-MS测定8种金属元素(Mn、Zn、Pb、La、Ce、Mo、Cr和Fe)的质量分数。依据分析结果,比较了消解程序的效果。结果表明,由10.0 mLHNO3对生物样品具有很好的消解能力,各元素的测定值与推荐值相符。     

ICP-MS分析地球化学样品的过程控制

通过对影响分析结果质量的消解方式、称样量、消解器皿及环境等因素进行分析,并采取相应措施,保证了分析结果的准确性、检出限,提高分析数据的重现性。     

Bulk stable light isotopic ratios in archaeological birch bark tars

The authors report a preliminary study of the light stable isotopic (δD, δ¹³C and δ¹⁸O) values for bulk archaeological birch bark tars, over a geographical (e.g. Greece to Norway) and chronological (9500–3000 BP) range. For δ¹³C an increase in fractionation with increase in latitude is observed in samples from Greece which are less depleted than those from northern Europe. There is no clear difference between the samples from northern Europe. There is no apparent trend in δ¹³C value with the ¹⁴C age of the sample. Due to biosynthetic fractionation all the samples are significantly depleted in ²H and enriched in ¹⁸O relative to the global meteoric water line. This study indicates that archaeological birch bark tar from Greece can be distinguished from those of northern Europe; this separation is probably based on the extreme geographical range of the samples examined here. But this does provide evidence that the birch bark tars were probably made locally rather than traded.     

不同消解方式等离子体质谱法测定生物样品中锗

采用湿法消解与干法灰化两种方式消解生物样品中锗,从实验结果可见,干法灰化较湿法消解具有较好的精密度及检出限.湿法消解准确度(RE)在-4.4％ ～-11.0％之间,干法灰化准确度在-17.2％～-28.4％之间,湿法消解准确度好于干法灰化.湿法消解精密度(RSD)在2.53％ ～ 17.74％之间,干法灰化精密度在0....     

富有机质地质样品Re-Os同位素体系研究进展

Re-Os同位素的研究在过去几十年取得了重要进展。Re、Os能够在各种不同类型的富有机质地质样品中富集,Re-Os同位素体系在各种富有机质样品的研究已成为同位素地球化学研究领域一个新的热点。文章介绍了Re-Os同位素体系研究应用于富有机质地质样品研究的原理及其地质样品种类,从风化淋滤和熟化两方面对Re-Os同位素体系的封闭性进行了说明,并且结合实例论述了Re-Os同位素体系应用于富有机质地质样品的重大意义,还对不同类型富有机质样品的采样和溶样方法进行了归纳。此外,还提出了当前富有机质地质样品Re-Os同位素研究亟待解决的问题,指出富有机质地质样品Re-Os同位素分析将成为解决地质难题一种新的有力工具。     

利用MC-ICPMS对水样中硼同位素比值的测定

采用Amberlite IRA-743硼特效树脂进行水溶液中硼的分离,对洗脱液温度、体积以及树脂动态交换容量等进行了实验.它的动态交换容量为4.2 mg/g,在室温条件下,用5 mL 2%HNO3可定量从树脂柱上洗脱被吸附的硼.采用Neptune型MC-ICPMS进行硼同位素组成的测定,1 μg/g浓度的硼标准溶液获得放大的信号强度约为0.7V,硼的化学分离过程有效避免了质量歧视效应.实验结果表明,MC-ICPMS对硼存在严重的记忆效应,通过采用5%HNO3-(1%HNO3 0.1%HF)-H2O-20%NH3H2O-H2O的交替清洗方法,可在约1 h内消除硼的记忆效应.在最佳仪器条件下,对含有250 ng硼的水样,可以快速测定硼的同位素组成,占δ11B测定的绝对偏差为0.4‰-0.5‰(SD).     

我国古食谱稳定同位素分析的影响因素及其蕴含的考古学信息

根据"我即我食"原理,生物体组织的稳定同位素组成与其食物来源密切相关。多样化食物资源与复杂的新陈代谢暗示着生物体组织的稳定同位素组成可能受到自然环境、人类活动以及自身生理健康等多因素的影响。对这些影响因素的综合评估不仅为更全面准确的重建古代人（或动物）的食谱提供重要依据,同时,结合考古学文化发展脉络,判断引起考古遗址出土生物体稳定同位素组成时空变化的主导因素,又可为揭示古代人地关系、人类活动以及社会经济发展等提供新的视角。为此,以我国古代独具特色的饮食文化为背景,在多因素影响机理论述基础之上,探讨可能影响我国古代人（或动物）稳定同位素食谱分析的各方面因素;同时,通过对不同影响因素的诠释,揭秘其背后隐藏的考古学信息。     

Pb isotopic zoning of K-feldspar megacrysts determined by Laser Ablation Multi-Collector ICP-MS: Insights into granite petrogenesis

This study investigates Pb isotopic zoning in magmatic K-feldspar megacrysts from the Monte Capanne pluton (Elba, Italy) using Laser Ablation Multi-Collector-ICPMS. The studied crystals provide an ideal opportunity to use in situ techniques to assess the extent of open-system processes and better characterize the components involved in the genesis of complex magma systems. Earlier investigations of the pluton identified the importance of magma mixing between mantle and crustal-derived magmas.The investigated K-feldspar megacrysts exhibit strong zoning in ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb, correlated with lead elemental variations. We interpret these variations as reflecting growth zoning, as opposed to secondary diffusive exchange. Despite a great variety of zoning patterns, we were able to correlate different events of megacryst growth, reflecting crystallization in a dynamic magma system. Our two-step model includes (1) growth of a granitic magma chamber by addition of low ²⁰⁸Pb/²⁰⁶Pb magma to a high ²⁰⁸Pb/²⁰⁶Pb magma contaminated with crustal material (i.e., the megacryst cores) and (2) recharge by mantle-derived magma (i.e., the megacryst rims). We interpret the thorogenic nature of the megacryst rims to reflect the mantle-derived component involved in the mixing process. Taking account of other data from the Tuscan Magmatic Province, the mantle source is inferred to have been metasomatized by continental material during subduction. TIMS Sr isotopic data from microdrilled cores in one megacryst provides general support for the model but show that the two isotopic systems are decoupled.     

地质样品Sr同位素激光原位等离子体质谱(LA-MC-ICP-MS)测定

Sr同位素在研究岩浆演化及其源区具有重要的示踪作用.MC-ICP-MS的出现为具有高Sr含量地质样品的激光原位Sr同位素测定变成了现实.本文利用Netpune MC-ICP-MS和193nm准分子激光联机,通过滨珊瑚、斜长石、磷灰石和钙钛矿等系列实验,建立了激光原位Sr同位素测定方法.实验结果表明,激光Sr同位素测定中Kr、Rb和稀土元素二价离子的干扰能够有效扣除,而钙聚合物的干扰在Neptune型MC-ICP-MS并不显著.不同激光参数的实验表明,大激光束斑产生更高信号强度,因而Sr同位素精度更高,同一激光束斑大小,激光脉冲频率对Sr同位素精度无明显影响.     

微波消解-电感耦合等离子体质谱测定玉米中铬、镉、铅

研究了微波消解-电感耦合等离子体质谱（ICP-MS）测定玉米中重金属元素的方法。详细讨论了微波样品溶液制备、质谱仪干扰扣除及校准等,在优化的试验条件下,根据国家标准参考物质（GBW10012）的分析结果评价方法的准确性。方法检出限为：Cd：0.003μg/g,Cr：0.04μg/g,Pb：0.1μg/g,相对标准偏差在2.5%-6.0%之间,加标回收率在90.9%-104.9%之间。     

辽南地区金矿床铅同位素组成特征

辽南地区是我国重要的金矿化集中区,区内产出大、中,小型金矿２０余处。简要叙述了猫岭,五龙,四道沟,岫岩,新房５个金矿床的地质概况。讨论了它们的铅同位素组成并划分为两大类：第一类具有正常铅的同位素组成,其成矿年龄与辽河群变质年龄相当;第二类具有异常铅的同位素组成。在铅构造模式图上,上述５个金矿床铅同位素组成具有壳源铅的特点。     

Lead isotopic composition and genesis of Phanerozoic metal deposits in China

Lead isotopic compositions of more than 130 galena specimens from Phanerozoic metal deposits in China have been analyzed with a standard deviation of less than 0.5%. The ranges of isotopic composition are from 17.8 to 19.3 for Pb²⁰⁶/Pb²⁰⁴, 15.2 to 16.0 for Pb²⁰⁷/Pb²⁰⁴ and 37 to 40.8 for Pb²⁰⁸/Pb²⁰⁴. These values overlap those of MORB, pelagic chemical sediments and intra-oceanic arcs of western Pacific in plots of Pb²⁰⁷/Pb²⁰⁴ vs. Pb²⁰⁶/Pb²⁰⁴ and Pb²⁰⁸/Pb²⁰⁴ vs. Pb²⁰⁶/Pb²⁰⁴. This indicates that mixing between mantle and crustal materials due to partial melting of the Pacific subduction slab is the principal mechanism for ore genesis. On the basis of global Precambrian conformable leads, together with that of Guanmenshan, Pengjiapu and Baiyun deposits in China, it is suggested that mantle lead was developed in a single stage with a (U²³⁸/Pb²⁰⁴) value of 7.8. If the ages of igneous rocks associated with these deposits are adopted as formation ages, the mean Th/U of the second stage of crust-mantle evolution can be calculated with a lead mixing model. The meanμ value of China continent is 9.98±0.78, which is in agreement with that of global conformable leads, 9.81±0.58. The mean Th/U ratio of 4.27 is distinctly larger than the global value (3.81), indicating that the China continent is rich in Th. Simultaneously, mean formation ages have also been obtained of the continental crusts in various regions, ranging from 3,000 to 3,800 m.y. and from 2,500 to 2,700 m.y., which are comparable with the age distribution of global Archaean cratons.     

Inverted clast stratigraphy in an eolian archaeological environment

Understanding the geomorphic history of eolian basins is important in interpreting the archaeological record and human responses to past environments. One hundred forty soil profiles were excavated and described in southern New Mexico and West Texas. Seven major late Quaternary stratigraphic units were found: La Mesa, eolian Jornada (I, II), eolian Isaacks' Ranch, eolian Organ (I, II, and III), Historical Blowsand, and the playa deposits of Petts Tank and Lake Tank. Each unit represents a period of landscape instability, eolian erosion, and concurrent deposition, followed by landscape stability and soil formation. Eolian erosion can form local surficial lag deposits if materials larger than the competence of the wind are present. However, erosional processes alone cannot explain the presence of older clasts at the surface with intact, younger deposits underneath. We propose a combination of processes: deflation in eolian windows, followed by lateral movement of clasts over areas that have not been deflated. The effects of these processes on artifact stratigraphy and archaeological interpretations could be significant. © 2002 Wiley Periodicals, Inc.     

石墨炉原子吸收光谱法测定血液中微量铅

研究了石墨炉测定血液中微量铅的适宜条件,用氘灯校正背景,磷酸二氢铵作基体改进剂,方法具有准确、快速、简便等优点,用于扬州妇幼保健院实际样品的测定,结果预示我们的环境不容忽视,血液中铅含量能够比较真实地反映生物个体受到的污染程度。     

Lead isotopic systematics of major river sediments: a new estimate of the Pb isotopic composition of the Upper Continental Crust

The lead isotopic composition of river sediments is reported in the present work for the Earth's major river basins, from old cratonic to young orogenic areas and from subarctic to tropical climates. Sediment samples from these large river basins provide a useful tool to calculate the average upper crustal composition because they are large-scale integrated samples of the weathering products of the present-day Upper Continental Crust (UCC). Two different and complementary calculations were done to estimate the average lead isotopic composition of the UCC. The first, based on the flux weighted average of particulate lead delivered by the rivers, gave values of 19.07, 15.74 and 39.35 for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios, respectively. To avoid over-estimating the contribution of orogenic areas, which produces a bias (because the flux of particulate lead depends strongly on the physical erosion rate), a second calculation was done by averaging with drainage areas of each river basin. This gave values of 18.93, 15.71 and 39.03 for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios, respectively. These direct calculations of the lead isotopic composition of the UCC are similar and are in agreement with previous estimates made using an indirect approach.     

改进的卡洛斯管溶样等离子体质谱法测定地质样品中低含量铂族元素及铼的含量

报道了一个改进的卡洛斯管溶样等离子体质谱法测定地质样品中铂族元素及Re含量的新方法。将封闭的卡洛斯管置于高压釜中,然后在高压釜中加水,密封在高压釜中的水在高温下产生的外压将会抵消卡洛斯管中由酸产生的内压,这样就可以避免传统的卡洛斯管在高温高压下可能发生爆炸的危险。由此可以加大取样量,降低铂族元素测定过程中的块金效应及检出限,使超低含量铂族元素的测定成为可能。12g样品在75mL卡洛斯管中用35mL王水于320℃溶解15h,基本上可以使各种地质样品中的铂族元素矿物完全溶解。一次溶样可以测定全部铂族元素及Re,全流程空白值极低,国际标样测定结果稳定可靠。     

ICP-MS测定地质样品中37个元素的准确度和长期稳定性分析

对Elan6100DRC型ICP-MS近五年来所测得的国际地质标样BHVO-1（玄武岩）和AGV-1（安山岩）中的37个元素的测定值以及仪器灵敏度的长期漂移情况进行了统计分析（共计146次）.结果表明,几年来ICP-MS所测数据的长期稳定性和准确度都较好,除个别元素Li（BHVO-1）、Be（BHVO-1））、Cr（AGV-1）、CS（BHVO-1）和Pb（BHVO-1）的相对误差（与参考值比较）接近或略大于10%外,绝大多数元素的相对误差和相对标准偏差（RSD,测定值之间,n=146）都在5%以内;仪器灵敏度并不是随着时间一直往下漂,有的是往上漂的,也有上下漂的,即使是在同一时间内,有的元素灵敏度往上漂,而有的往下漂.常用的内标法无法较好校正这种漂移,而需要采用内外标相结合的校正方法.不同批次,210个各种地质样品中Rb、Sr、Zr和Nb的XRF和ICP-MS分析结果对比情况表明,绝大多数样品中Rb、Sr、Zr和Nb的ICP-MS和XRF的测定值的相对误差小于10%.以上的分析结果表明,我们实验室所建立的以密闭高温高压消解技术为样品前处理方法,以模拟地壳样品中元素天然丰度比的基体匹配校正标准溶液为外标和以Rh为内标结合外标校正的ICP-MS多元素分析方法具有非常好的准确度和长期稳定性.     

Lead isotopic compositions in fault gouges and their parent rocks: implications for ancient fault activities

This is the first study on Pb stable isotopes in fault gouges and their parent rocks. We analyzed the composition of Pb isotopes and contents of U and Pb in 10 pairs of fault gouges and their parent rocks collected along several active faults in central Japan. Thorium-232-²⁰⁸Pb ages of two fault systems were determined as pre-Tertiary, which are consistent with the data from KAr ages and geological considerations.Naturally, the²³⁵U²⁰⁷Pb system is of little use for dating because the magnitude of difference in²⁰⁷Pb/²⁰⁴Pb between gouges and parent rocks is too small. It is found that the²⁰⁶Pb/²⁰⁴Pb can indicate the contribution of²⁰⁶Pb resulting from excess supplies of²²⁶Ra and²²²Rn along the fault. The excess²⁰⁶Pb accumulation rate corresponds to the average²²²Rn concentration in soil gas or groundwater through geological time since the gouge formation. A comparison of Quaternary fault activity and estimated Tertiary activity reveals the characteristics of each fault system.     

Carbon,hydrogen and nitrogen in carbonaceous chondrites: Abundances and isotopic compositions in bulk samples

Whole-rock samples of 25 carbonaceous chondrites were analysed for contents of C, H and N and δ¹³C, δD and δ¹⁵N. Inhomogeneous distribution of these isotopes within individual meteorites is pronounced in several cases. Few systematic intermeteorite trends were observed; N data are suggestive of isotopic inhomogeneity in the early solar system. Several chondrites revealed unusual compositions which would repay further, more detailed study. The data are also useful for classification of carbonaceous chondrites; N abundance and isotopic compositions can differentiate existing taxonomic groups with close to 100% reliability; Al Rais and Renazzo clearly constitute a discrete “grouplet”; and there are hints that both CI and CM groups may each be divisible into two subgroups.