三元体系CaCl2-SrCl2-H2O相平衡在高钙锶比卤水体系中分离提取氯化锶的应用

采用等温溶解平衡法测定了三元体系CaCl₂-SrCl₂-H₂O温度在353.15 K时共饱和点的溶解度。基于实验结果和文献已有报道的该体系多温下的相平衡数据,模拟了南翼山油田卤水中氯化钙和氯化锶在温度323.15 K下的分离实验。模拟钙锶分离实验结果表明,物质的量比为25.41∶1的CaCl₂和SrCl₂的混合溶液在323.15 K下蒸发结晶提纯后的固相中钙锶物质的量比降低为1.73∶1,SrCl₂的回收率为52.47%,将所得一次固相产品在323.15 K下溶解并再次蒸发后,钙和锶的物质的量比从1.73∶1降至1.1∶1,SrCl₂的回收率为78.67%,SrCl₂的总回收率为41.28%。     

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。     

扬子板块北缘马元铅锌矿地球化学特征及成矿机制探讨

位于扬子板块北缘的马元铅锌矿呈似层状产于震旦系灯影组角砾状白云岩中,矿石矿物为闪锌矿、方铅矿,脉石矿物有白云石、重晶石和少量石英、萤石、方解石等。本文着重对主要矿石及脉石矿物的锶、硫同位素和稀土元素地球化学特征进行对比研究,以探讨其成矿机制。早期沉淀产物闪锌矿流体包裹体及白云石的~(87)Sr/~(86)Sr比值为0.71111~0.71241,表明Sr来源以壳源锶为主;晚期重晶石~(87)Sr/~(86)Sr比值为0.70918和0.70971,表明重晶石中的锶主要来源于海水锶,有少量壳源锶加入。早期产物白云石、闪锌矿和方铅矿的稀土元素具有类似热卤水特征的明显正Eu异常(去掉特高值后平均值为1.99),而晚期重晶石则具有类似海水特征的负Ce异常(0.26)。硫同位素表现出富重硫(δ~(34)S12‰)的特点,表明硫可能主要来源于海相硫酸盐。还原硫的形成机制为硫酸盐的热化学还原作用,有机质如甲烷可能充当了还原剂。闪锌矿、方铅矿及重晶石的δ~(34)S值各自集中分布在较小的范围内且同位素分馏达到平衡,暗示金属、还原硫和硫酸根可能是同一成矿流体搬运的。矿质沉淀机制可能是地层中循环的富含放射性锶以及多种金属元素的成矿热卤水与下渗的海水(或大气降水)混合导致的。早期沉淀白云石、闪锌矿以及方铅矿的流体以热卤水为主,晚期与重晶石沉淀有关的流体则具有相对富含海水(或大气降水)的特点。     

New Reference Materials,Analytical Procedures and Data Reduction Strategies for Sr Isotope Measurements in Geological Materials by LA-MC-ICP-MS

Laser ablation multi-collector mass spectrometry (LA-MC-ICP-MS) has emerged as the technique of choice for in situ measurements of Sr isotopes in geological minerals. However, the method poses analytical challenges and there is no widely adopted standardised approach to collecting these data or correcting the numerous potential isobaric inferences. Here, we outline practical analytical procedures and data reduction strategies to help establish a consistent framework for collecting and correcting Sr isotope measurements in geological materials by LA-MC-ICP-MS. We characterise a new set of plagioclase reference materials, which are available for distribution to the community, and present a new data reduction scheme for the Iolite software package to correct isobaric interferences for different materials and analytical conditions. Our tests show that a combination of Kr-baseline subtraction, Rb-peak-stripping using βRb derived from a bracketing glass reference material, and a CaCa or CaAr correction for plagioclase and CaCa or CaAr + REE²⁺ correction for rock glasses, yields the most accurate and precise ⁸⁷Sr/⁸⁶Sr measurements for these materials. Using the analytical and correction procedures outlined herein, spot analyses using a beam diameter of 100 μm or rastering with a 50–65 μm diameter beam can readily achieve < 100 ppm 2SE repeatability ("internal") precision for ⁸⁷Sr/⁸⁶Sr measurements for materials with < 1000 μg g^-1 Sr.     

Chronology of Early to Mid-Pleistocene sediments in the northern North Sea: New evidence from amino acid and strontium isotope analyses

Sediments deposited during glacial-interglacial cycles through the Early to Mid-Pleistocene in the North Sea are chronologically poorly constrained. To contribute to the chronology of these units, amino acid racemization (AAR) and strontium (Sr) isotope analyses have been performed on samples from four shallow borings and one oil well along a transect in the northern North Sea. D/L Asp (aspartic acid) values obtained through reverse-phase liquid chromatography in the benthic foraminiferal species Elphidium excavatum is focused on because of consistent results and a good stratigraphic distribution of this benthic species. For the Early Pleistocene, an age model for the well 16/1–8, from the central part of the northern North Sea based on Sr ages allows for dating of the prograding wedges filling the pre-Quaternary central basin. A regional calibration curve for the racemization of Asp in Elphidium excavatum is developed using published ages of radiocarbon-dated samples and samples associated with the previously identified Bruhnes/Matuyama (B/M) paleomagnetic boundary and a Sr age from this study. Based on all the available geochronological evidence, samples were assigned to marine oxygen isotope stages (MIS) with uncertainties on the order of 10–70 ka.Sr ages suggest a hiatus of <2 million years (Ma) possibly due to non-deposition or low sedimentation between the Utsira Formation (Pliocene) and the Early Pleistocene. An increase in sedimentation rates around 1.5 ± 0.07 Ma (∼MIS 51) may partly be due to sediment supply from rivers from the south-east and partly due to the extension of ice sheet around 1.36 ± 0.07 Ma from the Norwegian coast to the central North Sea. A possible basin-wide glaciation occurred around 1.1 Ma (∼ MIS 32) (upper regional unconformity/top of unit Q4 in this study), resulting in erosion and regional unconformity. Two interglacials in the Norwegian Channel have been dated: the Radøy Interglacial to 1.07 ± 0.01 Ma (possibly MIS 31, the ‘super interglacial’), and the Norwegian Trench Interglacial to 0.50 ± 0.02 Ma (possibly MIS 13). A massive till unit identified at the same stratigraphic level in all shallow borings may partly represent an extensive MIS 12 glaciation. This study shows that the combined use of amino acid racemization data and Sr isotope chronology can refine the chronological ambiguities of Quaternary North Sea sediments related partly to the impact of glacial processes.