HAc溶解碳酸盐岩测定87Sr/86Sr值实验方法研究

传统的碳酸盐岩的sr同位素比值测定因为采用HCl溶样,往往导致非碳酸盐组分的溶解,引起测定值偏高,采用HAc溶样可以防止样品中非碳酸盐组分的溶解,同时也避免过多的杂质离子进入溶解液,从而使^87Sr／^86Sr测定值趋于准确和可靠;通过2.5mol/L HAc溶解碳酸盐矿样和4.0mol/L HCl溶解残渣样的最后质谱测定的^87Sr／^86Sr值比较,证实碳酸盐岩中非碳酸盐组分的^87Sr／^86Sr值较碳酸盐组分高。     

攀枝花青龙山昔格达组地层剖面微量元素地球化学特征及环境意义

对攀枝花青龙山昔格达组剖面进行了研究,分析了微量元素含量及其比值在剖面中的变化特征。结果表明,剖面中除Ba、Sr含量低于大陆上地壳外,其余元素含量均高于上地壳;w(Sr)/w(Cu)比值为1.81～4.50,δ(Ce)出现微弱负异常,反映整个剖面在沉积过程中,气候以温暖、湿润为主;w(Th)/w(U)比值偏高,且δ(Eu)显示中等程度负异常,反映剖面沉积环境总体偏还原性。样品中轻稀土富集,轻稀土含量与稀土总量呈显著正相关,说明地层中稀土元素特征主要受控于轻稀土的活动性,判断剖面沉积物为陆源特征。     

益气活血中药复方对冠心病患者治疗前后微量元素的影响

为探讨益气活血复方调整冠心病患者微量元素达到平衡,纠正异常相关因素的作用机制,选择冠心病患者80例及健康人5 7例,分别测定了冠心病患者治疗前后和健康人血清中微量元素含量。结果表明,益气活血复方组和西药组治疗后,均见Se,Cr,Mn ,Mg ,Sr,Cu,K ,Na,Ca等微量元素含量明显升高,Zn含量,w(Zn) /w(Cu) ,Fe含量明显下降,P <0 0 5或P <0 0 1。虽然益气活血复方组和西药组治疗后,元素上升与下降的趋势基本相同,但益气活血复方对元素的影响更明显,尤其是Zn,Co含量,w(Zn) /w(Cu)下降,Cu ,Cr,Mn,Sr含量上升,差异极显著,P <0 0 1。提示益气活血复方能调节体内微量元素的平衡,恢复心肌功能,防治冠心病     

Cu/Sr3Ti2O7的制备及其光催化分解水制氢活性

采用聚合合成法(PCM)合成出层状钙钛矿结构的Sr3Ti2O7, 进而负载Cu 离子, 制成Cu/Sr3Ti2O7催化剂. 以超纯水和甲醇牺牲剂体系的光催化分解反应为探针, 通过检测氢气生成速率评价了催化剂的光催化性能, 并借助光电子能谱(XPS)、X 射线衍射(XRD)分析、紫外-可见漫反射光谱(UV-Vis DRS)等手段对催化剂进行了表征. 实验结果表明, Cu 在催化剂中以多价态存在, Cu+和吸附氧有利于光生电子的转移. Cu/Sr3Ti2O7催化剂较之纯Sr3Ti2O7催化剂活性大大提高, Cu 最佳负载量为1.5%(w). 产氢速率可稳定在550-600 μmol·h-1. 还原过的Cu/Sr3Ti2O7催化剂产氢速率最高可达1140.8 μmol·h-1.     

锶掺杂对LaMnO3钙钛矿在稀燃条件下NO还原性能的影响

利用共沉淀法制备了La1-xSrxMnO3+λ钙钛矿氧化物粉末,研究了其在稀燃条件下对NO的还原活性.结果表明,添加少量Sr能使催化剂对NO的还原性能显著增加,在10% O2的富氧条件下, La0.7Sr0.3MnO3+λ催化剂对NO的转化效率在370 ℃达到60%. Sr含量过高,催化效率反而下降. XRD分析发现, Sr2+进入了钙钛矿晶格,部分取代La3+;过量的Sr2+导致Mn由三价变为四价,形成SrMnO3.热失重分析表明,随着煅烧温度升高,试样经历碳酸盐分解形成氧化物,氧化物结合形成钙钛矿的过程,在形成钙钛矿的过程中,伴随Mn变价失氧.     

“南永1井”礁相碳酸盐C,O,Sr,Pb同位素组成及其古环境意义探讨

“南永1井”礁相碳酸盐的O,C同位素组成可分为四段,它们的δ~(18)O(‰)和δ~(13)C(‰)平均值分别为:(Ⅰ)-5.0,-0.5;(Ⅱ)-7.7,-5.3;(Ⅲ)-6.4,-2.8;(Ⅳ)1.3,2.1.(Ⅱ)段的δ~(18)O值波动曲线以变化频率低、幅度小为特征,与布容期冰期-间冰期存在对应关系;(Ⅲ)和(Ⅳ)段的δ~(18)O和δ~(13)C值之间有正相关,在成因上与白云石化有关。△~(87)Sr和Pb同位素组成同样存在四分的特点。整个钻孔岩芯中△~(87)Sr的最大值和最小值以及全部正值都出现在第Ⅱ段。第Ⅳ段的Pb,sr同位素均呈现变化波动频繁的特点,在白云石化阶段有高μ值的Pb带入。礁相碳酸盐的O,C,Sr和Pb同位素组成记录了南海第四纪古气候、古环境变迁的历史。     

江西岩背火山侵入杂岩的地球化学特征和成因

本文对江西岩背火山侵入杂岩作了较详细的同位素和微量元素研究。它们具有相似的结晶年龄,较高的(~(87)Sr/~(86)Sr)_i和δ~(18)O值,高的~(207)Pb/~(204)Pb值,低的ε_(Nd)值和古老的Nd模式年龄。同时,它们还具有高的Rb/Sr和F/Cl值,弱的铈负异常和强的铕负异常。这些特征清楚表明,岩背火山侵入杂岩是同源岩浆演化的产物,其初始岩浆是由早、中元古代变质沉积岩经部分熔融形成的。     

Sr1-x Znx Y2 S4:Er3+,Eu2+荧光粉的合成与发光特性的研究

采用碳酸盐前躯体高温分解法合成了Sr1-xZnxY2S4:Er3+, Sr1-xZnxY2S4:Eu2+和Sr1-xZnxY2S4:Er3+, Eu2+红色荧光粉. XRD图谱表明, Zn2+掺杂量x<0.2 mol 时, 粉末样品为CaFe2O4型正交晶体. Zn2+离子在Sr1-xZnxY2S4:Er3+, Eu2+中的固溶量(x mol)对荧光粉的发射强度影响很大. 随着Zn2+离子掺杂浓度的增加, Sr1-xZnxY2S4:Er3+, Eu2+(SZYSEE)紫外区激发峰(200～413 nm)发生红移, 并与可见光激发带(413～600 nm)形成一个连续的宽带谱, 与紫外和GaN基LED芯片辐射都有良好的匹配性. 当Zn2+掺杂量为0.1 mol时, SZYSEE的发光强度达到最大, 其发光强度比未掺Zn2+的增强10.7倍. Sr0.9Zn0.1Y1.76S4:0.24Er3+, 0.006Eu2+是一种潜在的白光LED用红色荧光粉.     

磷灰石中锶同位素地球化学特征及其应用的研究

本文用质谱法精确地测定了我国各种类型花岗质岩石中若干磷灰石的Rb,Sr含量及Sr同位素组成;着重研究了各种磷灰石的Sr同位素地球化学特征及其在岩石成因、岩浆演化、岩带划分、构造运动、同位素地质年代学以及普查找矿等方面的应用。     

利用钐掺杂氧化铈提高燃料电池阳极活性

用浸渍法制备并采用交流阻抗、极化等技术考察了不同组成的Ni-Sm3＋掺杂的CeO2(SDC) 复合镍阳极的电化学性能及相应电池的功率输出性能.结果表明，SDC掺入镍阳极后,阳极极化过电位及电池的欧姆电阻显著减小.其中阳极过电位的减小与SDC掺入镍电极引起的三相界扩展有关，但SDC的掺入同时引起了电极反应活化能的增加,造成低温下Ni-SDC的极化过电位大于纯Ni电极.高温下,Ni-SDC阳极的阻抗谱由两个半圆组成，其中高频半圆随着SDC掺入量的增加而减小,而低频环与SDC的掺入量基本无关.低温下只观察到一个高频环.高频环可能对应三相界反应,而低频环可能对应氢的解离吸附及扩散.75％（w）Ni-25％（w）SDC/La0.9Sr0.1Ga0.8Mg0.2O3(LSGM)/Sm0.5Sr0.5CoO3(SSC)在所研究的电池中具有最大功率输出密度，其值在1073、973、873 K下分别达到1.1、0.43、0.14 W•cm－2.     

Intra‐ and inter‐tooth variation in strontium isotope ratios from prehistoric seals by laser ablation multi‐collector inductively coupled plasma mass spectrometry

Rationale

Strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) in modern‐day marine environments are considered to be homogeneous (~0.7092). However, in the Baltic Sea, the Sr ratios are controlled by mixing seawater and continental drainage from major rivers discharging into the Baltic. This pilot study explores if variations in Sr can be detected in marine mammals from archaeological sites in the Baltic Sea.

Methods

⁸⁷Sr/⁸⁶Sr ratios were measured in tooth enamel from three seal species by laser ablation multi‐collector inductively coupled plasma mass spectrometry (LA‐MC‐ICP‐MS). The method enables micro‐sampling of solid materials. This is the first time that the method has been applied to marine samples from archaeological collections.

Results

The analyses showed inter‐tooth ⁸⁷Sr/⁸⁶Sr variation suggesting that different ratios can be detected in different regions of the Baltic Sea. Furthermore, the intra‐tooth variation suggests possible different geographic origin or seasonal movement of seals within different regions in the Baltic Sea through their lifetime.

Conclusions

The method was successfully applied to archaeological marine samples showing that: (1) the ⁸⁷Sr/⁸⁶Sr ratio in marine environments is not uniform, (2) ⁸⁷Sr/⁸⁶Sr differences might reflect differences in ecology and life history of different seal species, and (3) archaeological mobility studies based on ⁸⁷Sr/⁸⁶Sr ratios in humans should therefore be evaluated together with diet reconstruction.

     

Simultaneous determination of mass-dependent isotopic fractionation and radiogenic isotope variation of strontium in geochemical samples by multiple collector-ICP-mass spectrometry.

We present a method to determine (88)Sr/(86)Sr and (87)Sr/(86)Sr simultaneously. The former variation reflects the mass-dependent isotopic fractionation through the physico-chemical processes, and the latter originates from beta(-)-decay of the parent nuclide (87)Rb as well as the mass-dependent isotopic fractionation. In order to determine the mass-dependent isotopic fractionation, the mass-discrimination effect on (88)Sr/(86)Sr was externally corrected by an exponential law using Zr. For the radiogenic growth of (87)Sr/(86)Sr, the mass-dependent isotopic fractionation effect on (87)Sr/(86)Sr was corrected by a conventional correction technique using the (88)Sr/(86)Sr ratio. The reproducibility of the (88)Sr/(86)Sr and (87)Sr/(86)Sr measurements for a high-purity Sr chemical reagent was 0.06 per thousand (2SD, n = 20) and 0.07 per thousand (2SD, n = 20), respectively. Strontium isotopic ratios ((88)Sr/(86)Sr and (87)Sr/(86)Sr) were measured on six geochemical reference materials (igneous rock: JB-1a and JA-2; carbonate mineral: JLs-1, JDo-1, JCp-1 and JCt-1) and one seawater sample. The resulting (87)Sr/(86)Sr ratios obtained here were consistent with previously published data within the analytical uncertainties. The resulting (88)Sr/(86)Sr ratios for igneous rock samples did not vary significantly within the samples, whereas the carbonate samples showed enrichments of the lighter Sr isotopes over the seawater sample. The (88)Sr/(86)Sr ratio of geochemical samples could reflect the physico-chemical processes for the sample formation. Also, a combined discussion of (88)Sr/(86)Sr and (87)Sr/(86)Sr of samples will render multi-dimensional information on geochemical processes.     

The determination and application of 87Sr/86Sr ratio in verifying geographical origin of wheat

As ⁸⁷Sr/⁸⁶Sr ratio plays a significant role in authenticating the geographical origin of foodstuff, it is important to identify where the ⁸⁷Sr/⁸⁶Sr signature in food comes from, and the methods of ⁸⁷Sr/⁸⁶Sr ratio analysis in food and environmental samples. Wheat with three genotypes, soil and groundwater samples were collected from three regions of China during harvest time of 2014. The ⁸⁷Sr/⁸⁶Sr ratios in the samples were determined by thermal ionization mass spectrometer in order to investigate the possible source of ⁸⁷Sr/⁸⁶Sr in wheat, and the concentrations of Rb and Sr in wheat and soils were also detected by inductively coupled plasma mass spectrometry and combined with ⁸⁷Sr/⁸⁶Sr ratio in order to trace the geographical origin of wheat. The ⁸⁷Sr/⁸⁶Sr ratio, the contents Rb and Sr, and Rb/Sr ratio of wheat and soil samples showed significant differences among three regions. The ⁸⁷Sr/⁸⁶Sr ratios and the concentrations of Rb and Sr in soils were higher than those in corresponding wheat. The ⁸⁷Sr/⁸⁶Sr ratio in wheat was identical to that corresponding soil NH₄NO₃ extracts (labile fraction of soil) and groundwater. Wheat uptake more Rb than Sr. 3D distribution of ⁸⁷Sr/⁸⁶Sr, Rb and Sr could identify wheat samples from different regions clearly. The ⁸⁷Sr/⁸⁶Sr ratio of wheat reflects the ⁸⁷Sr/⁸⁶Sr ratio of the associated environment including soil and groundwater. It is expected that the use the parameters of ⁸⁷Sr/⁸⁶Sr ratio, the contents of Rb and Sr will allow to trace geographical origin of wheat. Copyright © 2017 John Wiley & Sons, Ltd.     

Problems in obtaining precise and accurate Sr isotope analysis from geological materials using laser ablation MC-ICPMS

This paper reviews the problems encountered in eleven studies of Sr isotope analysis using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) in the period 1995–2006. This technique has been shown to have great potential, but the accuracy and precision are limited by: (1) large instrumental mass discrimination, (2) laser-induced isotopic and elemental fractionations and (3) molecular interferences. The most important isobaric interferences are Kr and Rb, whereas Ca dimer/argides and doubly charged rare earth elements (REE) are limited to sample materials which contain substantial amounts of these elements. With modern laser (193 nm) and MC-ICPMS equipment, minerals with >500 ppm Sr content can be analysed with a precision of better than 100 ppm and a spatial resolution (spot size) of approximately 100 μm. The LA MC-ICPMS analysis of ⁸⁷Sr/⁸⁶Sr of both carbonate material and plagioclase is successful in all reported studies, although the higher ⁸⁴Sr/⁸⁶Sr ratios do suggest in some cases an influence of Ca dimer and/or argides. High Rb/Sr (>0.01) materials have been successfully analysed by carefully measuring the ⁸⁵Rb/⁸⁷Rb in standard material and by applying the standard-sample bracketing method for accurate Rb corrections. However, published LA-MC-ICPMS data on clinopyroxene, apatite and sphene records differences when compared with ⁸⁷Sr/⁸⁶Sr measured by thermal ionisation mass spectrometry (TIMS) and solution MC-ICPMS. This suggests that further studies are required to ensure that the most optimal correction methods are applied for all isobaric interferences.     

Sedimentary characteristics of Mg-rich carbonate formations and minerogenic fluids of magnesite and talc occurrences in early Proterozoic in eastern Liaoning Province, China

There are large to superlarge magnesite and talc deposits occurring in Mg-rich carbon-ate formations distributed in the early Proterozoic Dashiqiao Formation in eastern Liaoning Prov-ince, China. The discovery of the sedimentary gypsum, isotopic geochemistry of δ~(18)O_(SMOW),δ~(13)C_(PDB), δ~(34)S_(VCDT) and Sr/Ba ratio of carbonate, talc, quartz and gypsums with field investigationand sample analysis in laboratory demonstrate that the formation of magnesite and talc deposits isclosely related to marine evaporates, which then underwent reworking of regional metamorphismand hydrothermal metasomatism. Metasomatic fluids originating from the paleoseawater played acontrolling role in the formation of talc deposits.     

Specificity and Origin of the Stability of the Sr Isotopic Ratio in Champagne Wines

The ⁸⁷Sr/⁸⁶Sr ratio of 39 Champagnes from six different brands, originating from the whole “Appellation d’Origine Contrôlée” (AOC) Champagne was analyzed to establish a possible relation with the geographical origin. Musts (i.e., grape juice) and base wines were also analyzed to study the evolution of the Sr isotopic ratio during the elaboration process of sparkling wine. The results demonstrate that there is a very homogeneous Sr isotopic ratio (⁸⁷Sr/⁸⁶Sr = 0.70812, n = 37) and a narrow span of variability (2σ = 0.00007, n = 37). Moreover, the Sr concentrations in Champagnes have also low variability, which can be in part explained by the homogeneity of the bedrock in the AOC Champagne. Measurements of the ⁸⁷Sr/⁸⁶Sr ratio from musts and base wines show that blending during Champagne production plays a major role in the limited variability observed. Further, the ⁸⁷Sr/⁸⁶Sr of the musts were closely linked to the ⁸⁷Sr/⁸⁶Sr ratio of the vineyard soil. It appears that the ⁸⁷Sr/⁸⁶Sr of the product does not change during the elaboration process, but its variability decreases throughout the process due to blending. Both the homogeneity of the soil composition in the Champagne AOC and the blending process during the wine making process with several blending steps at different stages account for the unique and stable Sr isotopic signature of the Champagne wines.     

Strontium isotope ratios (87Sr/86Sr) of tooth enamel: a comparison of solution and laser ablation multicollector inductively coupled plasma mass spectrometry methods

Strontium isotope ratios (87Sr/86Sr) in tooth enamel provide a means to investigate migration and landscape use in humans and other animals. Established methods for measuring (87)Sr/(86)Sr in teeth use bulk sampling (5-20 mg) and labor-intensive elemental purification procedures before analysis by either thermal ionization mass spectrometry (TIMS) or multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Another method for measuring 87Sr/86Sr is laser ablation MC-ICP-MS, but concerns have been expressed about its accuracy for measuring tooth enamel. In this study we test the precision and accuracy of the technique by analyzing 30 modern rodent teeth from the Sterkfontein Valley, South Africa by laser ablation MC-ICP-MS and solution MC-ICP-MS. The results show a mean difference in 87Sr/86Sr measured by laser ablation and by solution of 0.0003 +/- 0.0002. This degree of precision is well within the margin necessary for investigating the potential geographic origins of humans or animals in many areas of the world. Because laser ablation is faster, less expensive, and less destructive than bulk sampling solution methods, it opens the possibility for conducting 87Sr/86Sr analyses of intra-tooth samples and small and/or rare specimens such as micromammal and fossil teeth.     

白云鄂博稀土、铌钽矿物及其成因探讨

白云鄂博矿床赋存于元古代地层中,本文具体描述了矿物在矿床的部位和产状,区别出地层矿物和地层后的矿物,其中的热液交代现象具明显成矿特征,依据大地构造,岩浆活动,矿物共生组合,热液交代,成矿地质时代和持续时间等因素,认为稀土铌钽矿物成因是来自深源的硅酸碳酸岩浆演化分异的成矿热液,伴随着构造运动,侵入交元古代地层,长期多幕而成矿。     

肉类制品中微量锶的分离及^87Sr/^86Sr同位素比值测定

利用87Sr/86Sr同位素比值进行生物和古人类源区与迁徙的示踪是Sr同位素技术应用的新领域,也是考古研究和肉类食品溯源研究的新尝试。本研究对牛肉干粉采用酸溶、微波消解和灰化后硝酸提取等不同方法进行消解,比较了它们的离子交换分离效果和Sr同位素测定结果;用石英、石墨和瓷坩埚3种器皿对牛肉干粉进行灰化,检测了灰化器皿对87Sr/86Sr同位素比值的影响,从而确定了石英坩埚灰化的消解方法,建立了适合于肉类制品微量Sr的化学分离方法与87Sr/86Sr同位素比值测定方法。本方法包括肉类制品的石英坩埚灰化、离子交换分离和87Sr/86Sr比值的热离子化质谱测定。所建方法对肉类食品溯源和考古研究等领域富含有机质样品的Sr同位素比值测定具有普适性。