暴露测年样品中26Al和10Be分离及其加速器质谱测定

在已有实验流程基础上,建立并优化了石英样品中Be和Al提取、纯化等实验流程,设计的流程条件实验包括实验试剂、器皿和离子交换柱选择、离子交换树脂分离Be和Al时酸浓度选择等。结果表明,选择钢铁研究总院研制的⁹Be标准溶液作为¹⁰Be样品制备的载体;使用一次性实验器皿;选用4 cm规格的离子交换柱;用0.05 mol/L草酸和0.75 mol/L盐酸混合溶液洗脱吸附于阴离子树脂上的Al,可有效提取、纯化样品中的Be和Al。加速器质谱(AMS)测量结果显示,13组化学空白的¹⁰Be/⁹Be和²⁶Al/²⁷Al比值平均值分别为7.48×10^-15和1.96×10^-15,与国内已有宇宙成因核素实验室的结果(5×10^-15~8×10^-15)具有可比性。电感耦合等离子体发射光谱(ICP-AES)的测量结果表明,Be、Al回收率分别达90%和60%。基于新建立的实验流程分析了祁连山北侧金佛寺的一个岩石样品,获得了¹⁰Be和²⁶Al的暴露年代分别为(10.7±1.0) ka和(10.0±1.2) ka,与前人研究结果一致。     

14C测年技术新进展

¹⁴C测年技术的进展主要表现为3个方面：1)¹⁴C常规测定技术向高精度发展比较成熟，目前已可以普及；2)加速器质谱技术的建立和普及，使测定要求的样品碳量减少到mg级，甚至μg级，虽然目前的精度尚未超过常规方法，但由于所需样品量极少，测定时间短而工效高，大大拓宽了应用范围；3)高精度¹⁴C－树轮年龄校正曲线的建立，不但可将样品的¹⁴C年龄转换到日历年龄，而且对有时序的系列样品的¹⁴C年龄数据通过曲线拟合方法转换到日历年龄时年龄误差大为缩小。     

泥炭样品的AMS 14 C年龄测定: 全样、植物残体和孢粉浓缩物*

沉积物¹⁴ C的年龄测定一直是第四纪年代学研究的热点。文章对中国干旱、半干旱地区的内蒙古库伦泥炭剖面的泥炭全样、植物残体和孢粉浓缩物进行了AMS ¹⁴ C测年比较研究。从泥炭沉积物中提取用于AMS ¹⁴ C测年的孢粉浓缩物的关键步骤包括:过筛(125μm,63μm和10μm),重液浮选(比重1.9)及在180倍的体视显微镜下进行手工挑选。测年结果表明:孢粉浓缩物的测年值比同一层位的泥炭沉积物全样或植物残体的测年值老225~340年; 植物残体与孢粉浓缩物的测年结果较为接近。但是,距地表24~27cm处孢粉浓缩物给出了610~780A.D.的年龄值,远老于其下样点的年龄,而泥炭全样为现代样品,二者相差1255年,这可能与该样品孢粉纯度较低、掺杂有一些老碳物质燃烧后形成的微粒杂质有关。因此,提高孢粉纯度对孢粉浓缩物¹⁴ C测年至关重要。     

博斯腾湖湖泊沉积物光释光年代测量*

使用光释光年代学的单片再生法测量了博斯腾湖沉积剖面中碳酸盐泥及粉砂质泥底部的浅湖相灰色粉细砂和风成沙的年龄,对剖面上部碳酸盐层中陆生植物残体进行了AMS ¹⁴ C测年。通过不同测片的等效剂量(D_e)值的分布状况评价了样品的晒褪程度,选择不随灵敏度校正后的自然释光信号变化的相对集中的等效剂量(D_e)值计算了样品的埋藏年龄。通过这些年龄结果的对比,发现石英矿物的OSL年龄和AMS ¹⁴ C年龄在地层上是一致的,表明尽管在浅湖相细砂中存在不完全晒褪,但根据相对较小而集中的D_e值计算得到的年龄结果是可靠的。这些年龄结果和地层资料揭示末次冰消期以来至早全新世,博斯腾湖处于无水干盆地向深水湖泊转化的浅水湖泊状态,现代深水博斯腾湖大约形成于距今8ka前后。     

广东四会古森林地下生态系统14 C地层年代学研究*

运用AMS-¹⁴ C定年技术,研究了被埋藏水松古木的发育和死亡时间以及土壤剖面中总有机碳的¹⁴ C表观年龄和细根的¹⁴ C年龄。结果表明:该地区的水松古木开始发育和死亡的时间大致为4~3kaB.P. 。根据土壤有机碳¹⁴ C的表观年龄,该土壤剖面的¹⁴ C年代地层可以分为3层,分别为:1)表层,2634±32~3305±29aB.P. ; 2)腐殖层,3305±29~3813±31aB.P. ; 3)基底,3813±31~4544±33aB.P. 。基底、腐殖土层和表层的沉积速率分别为0.55mm/a, 4.33mm/a和0.26mm/a。 细根的¹⁴ C年龄变化范围为2290±29~3542±28aB.P. ,较同层位的土壤有机碳的年龄年轻。腐殖层土壤中有机碳含量高达33 ％ ~46 ％ ,大多数有机碳仍处于未分解状态。该地区自4~3kaB.P.以来,环境演化可能经历了由陆到沼泽再到被水淹没最后又变成陆地的过程,植被从以水松为优势种的森林群落演化成当前以常绿阔叶林为主的森林生态群落,气候和海平面变化、地质构造运动和人类活动是这种环境演化的主要驱动因子。     

柴达木盆地察尔汗贝壳堤剖面年代学研究*

利用常规¹⁴ C、加速器(AMS)和²³⁰ Th等测年方法,对位于青藏高原东北部柴达木盆地察尔汗古湖贝壳堤剖面化石贝壳、湖泊沉积(包括现代沉积)样品有机质(包括碱性残留和胡敏酸组分)、碳酸盐(CaCO₃)和剖面顶部石盐(NaCl)晶体在不同实验室进行了系统的实验研究,探讨了不同样品测年结果的可靠性和精确性,并通过与已有研究结果的对比,对柴达木盆地贝壳堤剖面记录的察尔汗古湖高湖面演化历史进行了探讨,得出察尔汗古湖高湖面形成于约39.7~17.5 ¹⁴ C kaB.P. ; 研究证明柴达木盆地沉积物中有机质含量很低,且主要来源于菌藻类等低等藻类和微生物,受老碳和溶解物质影响强烈,因此必须经过多种方法综合测年才能比较可靠地确定所测样品的形成年代; 测年结果的不确定性不仅来源于样品自身元素(同位素)的特性和沉积过程中再沉积作用的影响,也可能源自于放射性¹⁴ C产生过程的不稳定性; 对比发现贝壳化石老于同层位有机质¹⁴ C年龄15~18ka,这可能与柴达木盆地所处的特殊地理位置和巨大的古湖泊面积及水体有关; 同时,不平衡铀系测年在确定开放体系矿物晶体年代应用中的可靠性尚须进一步深入分析,其机理也还需要探讨和实验研究。     

基于大样本14 C测年资料的 华北平原沉积速率研究*

华北平原是我国研究程度较高的地区,历年来积累了大量的¹⁴ C测年资料。从这些资料中尽可能地提取沉积速率的信息,并进而研究华北平原沉积速率的变化及其与流域自然和人文环境变化之间的关系,是一个有重要意义的问题。利用华北平原456个地点的¹⁴ C年龄与样品埋深资料,计算出了各个样品所在层位沉积以来的平均沉积速率(R_T),以此来近似反映各地点的平原沉积速率,并据此建立了R_T随时间的变化关系。从古至今, R_T有明显的增大趋势。以点群的上包线反映各时代的平原最大沉积速率,该指标可以反映华北平原的主体即黄河下游冲积平原的沉积速率。发现了最大平均沉积速率随时间变化过程中的4个突变点,分别为10000aB.P. , 5000aB.P. , 3000aB.P. 和1400aB.P. 。4个突变点将上包线分成5条折线,由此可以将近4万年以来的变化分成5个阶段。从古至今,5条折线的斜率增大,反映了平原沉积的加速过程; 并对4个突变点的成因进行了解释。阶段1,阶段2和阶段3沉积速率的加速是由自然原因造成的; 阶段4和阶段5沉积速率的加速则是由自然和人为原因共同造成的。从456个地点的¹⁴ C年龄与样品埋深资料中提取了距今4万年以来华北平原的平均沉积速率的信息,计算出平均沉积速率为0.9mm/a。按此求出,近4万年以来华北平原的沉积总厚度为36m。     

岱海14 C测年的现代碳库效应研究*

碳库效应的复杂性是影响建立湖泊沉积物高精度年代序列的一大障碍。本项研究通过我国内蒙古半干旱区封闭湖泊表层沉积物、湖水、现生沉水植物狐尾藻、现生鲤鱼鱼骨和湖岸表层土壤等一系列样品的¹⁴ C年代测定,表明现代岱海确实存在碳库效应。碳库效应年龄因湖水盐度在湖区的不均而有所变化,岱海西部湖区弓坝河径流补给量大,湖水盐度较东部稍低,碳库效应年龄也略小于东部湖区。表层沉积物中有机质包含浮游生物和沉水植物的混合信息,因而其碳库效应年龄较沉水植物年龄轻,岱海湖心表层沉积物碳库效应年龄在2000a左右。这一碳库效应年龄较通过沉积钻孔¹⁴ C年龄线性回归获得的年龄偏大,可能的原因是在时间序列上碳库效应并非恒定。     

湖泊沉积物的14 C和光释光测年* ——以固城湖为例

富含有机质的湖泊沉积物被认为是¹⁴ C测年建立古环境记录年代标尺的理想材料,光释光测年方法近年开始应用于水成沉积物的定年。应用¹⁴ C和光释光两种方法对江苏固城湖湖心钻孔岩芯进行了年龄测定,结果表明全样有机质的¹⁴ C年龄与石英的光释光年龄存在系统差异,后者较前者年轻约2000年。系统光释光测年研究排除了光释光年龄低估的可能性,所以,二者的差异可能是湖泊沉积物碳库效应的反映。     

黄土和红粘土中宇宙成因核素定年的潜力: 10 Be浓度与化学成分的关系*

宇宙成因核素¹⁰ Be(半衰期1.5Ma)不但是古环境变化的示踪剂,而且具有确定地质年龄的能力。80个全岩样品的¹⁰ Be和化学分析数据表明,黄土高原约6Ma以来的红粘土和黄土序列中年龄校正的¹⁰ Be浓度与沉积物粒度和风化程度的化学指标具有显著的关系。根据这种关系建立的¹⁰ Be浓度与化学指标的经验回归线性模型,可以估计红粘土和黄土形成时的¹⁰ Be浓度,确定红粘土和黄土形成的¹⁰ Be放射性年龄。     

湖芯沉积物揭示的末次冰消开始时期 普莫雍错湖区环境变化*

文章讨论了末次冰消开始时期青藏高原南部普莫雍错湖芯沉积反映的环境暖湿化以及原因。通过对现代湖泊和周边河流水文状况调查,发现流域内发育众多冰川,冰川融水构成维持湖面稳定的重要来源;湖面以及湖泊沉积环境的变化与冰川融水以及相应的温度改变具有密切的联系。利用湖泊沉积岩芯PM-1孔,通过加速器¹⁴ C测年和粒度、元素、碳酸盐含量、总有机碳以及有机碳同位素、总氮、分子标志化合物、孢粉等环境指标的分析,发现在16.4~15.4cal.kaB.P.有大量流水进入湖泊,使湖面扩大,湖水加深;流域地表产生大量有机碎屑,并被流水带入湖泊进行沉积;流域内的喜湿植被得以发展。该时段湖泊扩张、陆源植被发展的原因一方面得益于冰期过后气候向温暖湿润方向转化,另一方面温度上升带来大量冰川融水则可能具有更加重要的影响,对于深入理解当前青藏高原冰川普遍退缩和一些湖泊的水面上涨具有重要的参考价值。     

放射性碳测年国际比对活动的初步结果

中国科学院地球环境研究所^14C实验室作为中国唯一的代表参加了第四届放射性碳测年国际比对活动(FIRI），取得了比较优异的成绩。初步分析了本届比对活动的测年结果，得出如下结论：不同的^14C测年方法对测年结果无明显的影响，不同现代碳标准的选择对大部分样品的测年结果有较明显的影响，而采用不同的本底物质仅对老年龄样品的定年有显著影响；加速器质诺测年法在各种^14C测年方法中最准确、精度最高，正逐渐成为国际^14C测年方法的主流。     

东昆仑断裂带库赛湖段晚第四纪古地震研究*

对东昆仑断裂带库赛湖段进行了断错地貌填图和古地震探槽揭露研究。除2001年昆仑山口西8.1级地震外,共揭露出9次古地震事件,它们的年龄分别为31900±1923aB.P. , 27990±1681aB.P. , 23635±1427aB.P. , 20345±1225aB.P. , 16865±1018aB.P. , 12935±774aB.P. , 9730±592aB.P. , 6955±425aB.P.和3100±201aB.P.;古地震重复间隔分别为3910±2554a,4355±2205a,3290±1881a,3480±1593a,3930±1279a,3205±975a,2775±728a,3855±470a和3100±201a。研究结果表明,库赛湖段晚第四纪古地震活动具有准周期性,其平均重复间隔为3544±416a。发生在距今3100年前的倒数第1次古地震事件的离逝时间与重复间隔非常接近,这意味着2001年11月14日发生在库赛湖段的8.1级大地震为该断裂地震活动在准周期上的再现。高的滑动速率和长周期复发间隔表明库赛湖段活动习性以重复发生大地震为特征。     

东昆仑断裂带西大滩段全新世古地震研究*

对东昆仑断裂带西大滩段进行了断错地貌填图和古地震探槽揭露,共揭露出6次古地震事件,它们的年龄分别为10302±651aB.P. , 8650±500aB.P. , 7160±506aB.P. , 2830±170aB.P. , 1985±121aB.P.和1540±92aB.P. ;古地震重复间隔分别为1652±820a,1490±711a,4330±534a,845±209a和445±152a。研究发现,西大滩段全新世古地震活动具有丛集现象和重复间隔时间的分段性,第1丛集期在10300~7100aB.P.期间,平均重复间隔1571±543a,第2丛集期在2800~1500aB.P.期间,重复间隔400~800a左右,平均重复间隔645±129a,两个丛集期间隔4300a。西大滩段全新世地震活动规律对昆仑山地区未来地震危险性评估具有重要意义。     

Fluid and silicate glass inclusions in ultramafic and mafic xenoliths from Hierro,Canary Islands: implications for mantle metasomatism

Fluid and solid inclusions have been studied in selected samples from a series of spinel-bearing Crdiopside-and Al-augite-series ultramafic (harzburgites, lherzolites, and olivine-clinopyroxene-rich rocks), and gabbroic xenoliths from Hierro, Canary Islands. In these samples several generations of fluid inclusions and ultramafic-and mafic-glass inclusions may be texturally related to different stages of crystal growth. The fluid inclusions consist of pure, or almost pure, CO₂. The solid inclusions in the ultramafic xenoliths comprise early inclusions of devitrified ultramafic glass, sulphide inclusions, as well as polyphase inclusions (spinel+clinopyroxene±glass±other silicates) believed to have formed from trapped basaltic melts. Vitreous basaltic glass±CO₂±sulphide±silicates are common as secondary inclusions in the ultramafic xenoliths, and as primary inclusions in the gabbroic xenoliths. Microthermometry gives minimum trapping temperatures of 1110° C for the early ultramafic-and mafic-glass inclusions, and a maximum of 1260–1280° C for late inclusions of host basaltic glass. In most samples the CO₂ inclusions show a wide range in homogenization temperatures (-40 to +31° C) as a result of decrepitation during ascent. The lowest homogenization temperatures of about-40° C, recorded in some of the smallest CO₂ inclusions, indicate a minimum depth of origin of 35 km (12 kbar) for both the Cr-diopside-and Al-augite-series xenoliths. The gabbroic xenoliths originate from a former magma chamber at a depth of 6–12 km.Contribution no. 100 of the Norwegian programme of the International Lithosphere Project     

青海湖冰后期以来古气候波动模式的研究

本文根据青海湖QH-16A近代沉积物岩芯中介形虫壳体的δ¹⁸O、δ¹³C、Mg/Ca和Sr/Ca值分析,讨论了青海湖区12,000年以来的气候特征。利用氧、碳同位素的相关性和相对温度、盐度变化曲线建立了青海湖区冰后期以来的气候波动模式,划分出5个气候期和23个气候阶。通过与布列特-谢尔南德冰后期气候方案对比,证实该气候波动模式具有世界性。     

A rapid method for preparing low volume CH4 and CO2 gas samples for 14C AMS analysis

¹⁴C measurements of CH₄ in environmental samples (e.g. soil gas, lake water, gas hydrates) can advance understanding of C cycling in terrestrial and marine systems. The measurements are particularly useful for detecting the release of old C from climate sensitive environments such as peatlands and hydrate fields. However, because ¹⁴C CH₄ measurements tend to be complex and time consuming, they are uncommon. Here, we describe a novel vacuum line system for the preparation of CH₄ and CO₂ from environmental samples for ¹⁴C analysis using accelerator mass spectrometry (AMS). The vacuum line is a flow-through system that allows rapid preparation of samples (1 h for CH₄ and CO₂, 30 min for CH₄ alone), complete separation of CH₄ and CO₂ and is an easy addition to multipurpose CO₂ vacuum lines already in use. We evaluated the line using CH₄ and CO₂ standards with different ¹⁴C content. For CH₄ and CO₂, respectively, the total line blank was 0.4 ± 0.2 and 1.4 ± 0.6 μg C, the ¹⁴C background 51.1 ± 1.2 and 48.4 ± 1.5 kyr and the precision (based on pooled standard deviation) 0.9‰ and 1.3‰. The line was designed for sample volumes of ca. 180 ml containing 0.5–1% CH₄ and CO₂, but can be adjusted to handle lower concentration and larger volume samples. This rapid and convenient method for the preparation of CH₄ and CO₂ in environmental samples for ¹⁴C AMS analysis should provide more opportunities for the use of ¹⁴C CH₄ measurements in C cycle studies.     

Accurate and High‐Precision Determination of Boron Isotopic Ratios at Low Concentration by MC‐ICP‐MS (Neptune)

We report an approach for the accurate and reproducible measurement of boron isotope ratios in natural waters using an MC‐ICP‐MS (Neptune) after wet chemistry sample purification. The sample matrix can induce a drastic shift in the isotopic ratio by changing the mass bias. It is shown that, if no purification is carried out, the direct measurement of a seawater diluted one hundred times will induce an offset of ?7‰ in the isotopic ratio, and that, for the same concentration, the greater the atomic mass of the matrix element, the greater the bias induced. Whatever the sample, it is thus necessary to remove the matrix. We propose a method adapted to water samples allowing purification of 100 ng of boron with a direct recovery of boron in 2 ml of 3% v/v HNO₃, which was our working solution. Boron from the International Atomic Energy Agency IAEA‐B1 seawater reference material and from the two groundwater reference materials IAEA‐B2 and IAEA‐B3, was chemically purified, as well as boron from the certified reference material NIST SRM 951 as a test. The reproducibility of the whole procedure (wet chemistry and MC‐ICP‐MS measurement) was ± 0.4‰ (2s). Accuracy was verified by comparison with positive‐TIMS values and with recommended values. Seawater, being homogeneous for boron isotope ratios, is presently the only natural water material that is commonly analysed for testing accuracy worldwide. We propose that the three IAEA natural waters could be used as reference samples for boron isotopes, allowing a better knowledge of their isotopic ratios, thus contributing to the certification of methods and improving the quality of the boron isotopic ratio measurements for all laboratories.     

IAGC and IAEA Interlaboratory Comparisons of Geothermal Water Chemistry: The Propagation of Uncertainty in the Reservoir pH Calculation

A statistical evaluation of the results of geochemical analyses of geothermal waters during interlaboratory comparison programmes of the International Association of Geochemistry and Cosmochemistry (IAGC) and International Atomic Energy Agency (IAEA) was performed to estimate the uncertainty of measurement of pH, electrical conductivity, Na⁺, K⁺, Ca2⁺, Mg²⁺, Li⁺, Cl^?, HCO₃^?, SO₄^2?, SiO₂ and B. The uncertainty of measurement was found to increase exponentially with decrease in value (concentration) for all the parameters except for pH, electrical conductivity and SiO₂ and was of the same order of magnitude as the concentrations for values of less than 1 μ ml^?1. There was an overall uncertainty of ± 2.5% in the measurement of pH and ± 30% in SiO₂. For all the other chemical species the uncertainty data were modelled by exponential curves. The sample IAEA14 was prepared by dissolving commercial reagents (i.e., represents a solution of known composition). Thus, the calculated values are considered to be the conventional true values for each chemical parameter. The difference between the measured mean of the data submitted by participating laboratories and the conventional true value for each parameter (i.e., bias of submitted measurements) for the species Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl^? and SO₄^2? was ‐3.5, ‐1.1, ‐13.3, ‐53.6, ‐12.6 and ‐86.6%, respectively. The observed bias was of the same order of magnitude as statistical fluctuations (1s) for Na⁺ and K⁺, but significantly higher for Ca²⁺, Mg²⁺, Cl^? and SO₄^2?. Two methods, uncertainty interval and GUM (“guide to the expression of uncertainty of measurement”) were used to propagate uncertainty in the pH calculation of geothermal reservoir fluid. The application of the methods is illustrated by considering the IAEA10 and IAEA11 samples analysed in the interlaboratory comparisons as separated geothermal waters at atmospheric pressure.