Ba同位素分析方法综述

随着实验技术的进步以及多接收电感耦合等离子体质谱仪（MC-ICP-MS）和热电离质谱仪（TIMS）的发展,近年来Ba 同位素的分析方法取得了显著进展。分析精度（δ^138/134Ba,2SD）从之前的1 ‰ 提高到好于0.05 ‰。文章综述了近年来高精度Ba 同位素分析方法（溶液法）的发展历程,总结了国内外实验室关于不同类型样品的消解、Ba 元素化学纯化流程以及Ba 同位素质谱测定等方法,并对国内外多个实验室已发表的各类标准物质的Ba 同位素组成进行统计。研究结果可为Ba 同位素激光原位分析提供参考,为后续分馏机理解析和应用研究提供技术支撑。     

全新世黄土剖面Li/Ba值变化及其古气候意义

对陕西华县老官台全新世黄土和古土壤剖面的化学分析表明:Li和Ba两种化学元素含量受后期风化成壤作用的控制而发生分离,Li在风化剖面中残留而相对富集,表现为残留富集的特点;而Ba在整个剖面中的变化相当显著,随成壤强度的增强而大量淋失,导致其含量急剧减少,表现为极强的活动性。所以Li/Ba值能较好地反映风尘沉积物在后期经历的风化成壤强度。由于控制风尘沉积物成壤过程的主导因素是降水量的多少,而影响黄土高原及周边地区降水量的主导因素是东亚季风环流,因此Li/Ba值变化实际上反映了东亚季风系统的变化。Li/Ba值是再现古气候环境变化的良好替代指标,这在其与磁化率和Rb/Sr值良好的对应关系中得到有力的证实。     

南海北部珊瑚Ba/Ca比值的季节变化及其环境意义

利用等离子体普技术分析了取自海南岛南部沿岸的现代演珊瑚高分辨率的Ｂａ／Ｃａ。结果表明,该珊瑚的Ｂａ／Ｃａ比值具有明显的双峰态的季节变化,其中春季和秋季Ｂａ／Ｃａ比值较镐,而冬、夏两季则较低。海南岛南部及邻近地区季节降雨的变化所控制的原Ｂａ输入是这些珊瑚Ｂａ／Ｃａ比值变化的重要控制因素,而该区夏季相对较镐的表层海水生产力可能也对其有重要影响。     

Assessment of water quality for drinking and irrigation purposes: a case study of Başköy springs (Ağlasun/Burdur/Turkey)

It is important to know the quality of water resources for drinking, domestic and irrigation in the rural area. Because, in recent times, there has been increased demand for water due to population growth and intense agricultural activities, so, hydrogeochemical investigations come into prominence for the groundwater use. The purpose of this paper is to evaluate water quality of Ba?köy springs for both drinking and irrigation purposes. The geochemical processes and quality of springs were followed as seasonal in the study area. In view of geochemical classification, springs are Ca-Mg-HCO₃ water type for both seasons. Comparison of geochemical data shows that majority of the spring samples are suitable for drinking water. On the other hand, chemical indexes of springs with various classifications were calculated for irrigation purposes. According to the classifications (electrical conductivity, total dissolved solids, total hardness, salinity hazard, percent sodium, sodium adsorption ratio, residual sodium carbonate, residual sodium bicarbonate, permeability index, potential salinity, soluble sodium percentage, magnesium ratio, and Kelly’s ratio), Ba?köy springs are suitable for irrigation purposes. However, water quality of Çaygözü spring is different the other springs due to the high electrical conductivity and total dissolved solids. Also, groundwater mineralization processes and rock–water interaction are controlled with bivariate diagrams of major elements.     

The application of δ13C and C/N ratios as indicators of organic carbon sources and paleoenvironmental change of the mangrove ecosystem from Ba Lat Estuary, Red River, Vietnam

In this study, two sediment cores (~70 cm) were collected from separate mangrove forests straddling the Ba Lat Estuary, Red River of northern Vietnam, to examine the origins of sedimentary organic carbon (SOC) and reconstruct the paleoenvironment. In addition, mangrove leaves and particulate organic matter were collected and measured for δ¹³C to trace the origins of SOC. The cores were analyzed by high-resolution sections for δ¹³C, TOC, C/N ratios, sediment grain size, water content, and porosity, with values of δ¹³C, TOC, and C/N ratios ranging from −28.19 to −22.5‰, 2.14–30.94 mg/g, and 10.29–18.32, respectively. The δ¹³C and TOC relationship indicated that there were some small residual effects of diagenetic processes on TOC and δ¹³C values in mangrove sediments. However, the shifts of δ¹³C and C/N ratios from the bottom to the surface sediment of the cores explained the change in organic matter sources, with values of C/N > 12 and δ¹³C < −25‰, and C/N < 12 and δ¹³C > −25‰ indicated terrestrial (e.g., mangrove litter) and marine phytoplankton sources, respectively. The covarying δ¹³C, C/N ratios, and sediment grain sizes during the past 100 years in sediment cores showed that the paleoenvironment may be reconstructed into three environments (subtidal, tidal flat, and intertidal mangrove). General trends in δ¹³C and C/N followed a gradual increase in the C/N ratio and a concomitant decrease in δ¹³C from the subtidal, through to tidal flat, and to the intertidal mangrove. δ¹³C and C/N ratios are therefore effective in measuring the continuum of environmental change in mangrove ecosystem.     

V和Ba同位素分析方法综述

随着多接收电感耦合等离子体质谱(MC-ICP-MS)的应用,金属稳定同位素的分析方法不断得到改善和突破,这使得金属稳定同位素地球化学成为国际上新兴的地球科学方向。本文以V和Ba同位素为代表,详述了这两个体系近年来分析方法的进展。重点介绍了中国科学技术大学金属稳定同位素实验室建立的高精度的V同位素分析方法[δ~(51)VAA的长期外部测量精度好于±0.1‰(2SD)],以及将SRM3104a作为基准标样的Ba同位素分析方法[δ~(137/134)Ba_(SRM3104a)长期外部测量精度优于±0.05‰(2SD)]。     

MC-ICP-MS高精度Ba同位素分析方法

<正>Ba在岩浆作用过程中是不相容的微量元素,在陆壳中的含量远高于地幔。过去针对碱土金属同位素(例如Mg、Ca、Sr)体系的研究表明,这些同位素在各种高温和低温的地球化学过程中可以发生分馏。因此,我们预测Ba同位素在风化作用、热液活动和生物地球化学等一系列过程中也可能产生同位素分馏,例如,已有研究发现低温环境中Ba同位素分馏可以高达0.5‰[1]。当高含量、大分馏的地壳物质随俯冲板块进入     

La—Ba同位素计时法

1985年10月,笔者访问日本了解到:从1983年以来,增田等人在发表的La-Ce稀土同位素测年方法的基础上,又进一步采用~(138)La(?)~(138)Ba电子俘获衰变体系,研究了另一个目前认为是最新的放射性同位素地质年代学测定方法——La-Ba计时法。虽然这一新的计时法目前离达到实用阶段尚有许多工作要做,但是它无疑丰富了稀土同位素地球化学和同位素地质年代学的研究内容,意义是深远的。现将增田等人所研究的这一新的计时法简介如下:     

Co-precipitation of Sr2+ and Ba2+ with aragonite by membrane diffusion of CO2 between 10 and 50 °C

Aragonite is precipitated by a new CO₂-diffusion technique from a Ca²⁺–Mg²⁺–Cl⁻ solution between 10 and 50 °C. Crystallisation of aragonite instead of calcite occurs by maintaining a [Mg²⁺]/[Ca²⁺] ratio of 2 in the fluid. The dissolved inorganic carbon (DIC) is received by diffusion of CO₂ through a polyethylene membrane (diffusion coefficient: D_CO2=10^−6.4 cm² s⁻¹ at 19 °C). It is suggested that significant amounts of DIC may be transferred by diffusion of CO₂ in natural systems if the CO₂ gradient is high. The CO₂-diffusion technique is used as a kind of simple mixed flow reactor for the co-precipitation of barium and strontium with aragonite. The distribution coefficients of Ba²⁺ and Sr²⁺ decrease from 10 to 50 °C according to D_Ba,a*=2.42−0.03595T (°C) and D_Sr,a*=1.32−0.005091T (°C). At 25 °C, the distribution coefficients are D_Ba,a*=1.5±0.1 and D_Sr,a*=1.19±0.03. The effect of temperature on D_Ba,a* is about one order of magnitude higher versus that on D_Sr,a*. Thus, Ba²⁺ may be a potential paleotemperature indicator if the composition of the solution is known.     

Formation of helictite in the cave Dragon Belly (Sardinia,Italy)—Microstructure and incorporation of Mg,Sr, and Ba

In the Dragon Belly cave helictites, a special type of irregular speleothem, are found, which grew on stalactites in all vertical and horizontal directions without any affinity to gravity. Microstructural and mineralogical analyses of this stalactite–helictite system indicate that its evolution is initiated by clogging of the central stalactite channel at its tip, probably when the cave was flooded by muddy water. Clogging caused the formation of secondary channels (≈0.2 mm in diameter) for water passage through the outer surface of the stalactite, where helictites start to grow. The secondary channel passes into the central channel of the helictite.The helictites consist of stacked idiomorphic calcite crystals with uniform orientation. Growth of calcite is essentially controlled by water transfer through the central channel and via canalicules (narrow channels of ≈0.05 mm in diameter) following the crystal boundaries of the calcite mesocrystal induced by capillary hydrostatic forces. At straight parts of the helictites calcite crystals are almost uniform in size, but at bended parts crystals are significantly smaller inside (≤0.1 mm in length) than outside of the bend (≤0.5 mm). It is proposed that the difference in calcite volume (larger crystals) vs. the inside of the bend leads to a helix form, which explains the origin of the term helictite.The Sr and Ba concentrations measured by laser ablation along helictites can be explained by cation incorporation during calcite precipitation close to equilibrium. Dilution effects caused by seasonality control the elemental distribution in the helictite, which result in a positive correlation between Sr and Ba. Variability of Mg is unrelated with Sr and Ba, and is probably due to the incongruent dissolution of Mg–calcite from the host rock.     

Paleontological,mineralogical and chemical studies of syngenetic and epigenetic Pb–Zn–Ba–P mineralizations at the stratotype of the K/P boundary (El Kef area,Tunisia)

The El Kef area, Tunisia, is host of the official stratotype of the K/P boundary and of a complex metallic and non-metallic mineralization at Djebel Sekarna, encompassing syn(dia)genetic shale- and carbonate-hosted Zn–P and epigenetic Pb–Zn–Ba ore mineralizations. Micropaleontological, geological, mineralogical, and chemical studies (major and minor elements, C- and O-isotopes) of Upper Santonian to Lower Eocene calcareous-siliciclastic sediments resulted in a subdivision of this mineralization into eight mineralizing stages. Stages 1 and 2 (late Cretaceous–early Paleogene) are representative of syn(diagenetic) shale- and carbonate-hosted sulfidic and siliceous (Fe)–Zn–P mineralization deposited in shallow marine to slightly brackish sediments. Stages 3–5 (early Eocene respectively—pre- and post-Nummulites involutus-exilis zones) are representatives of epigenetic sulfidic and sulfatic (Fe)–Zn–Pb–Ba mineralizations at temperatures as high as 170/200°C and stages 6 and 7 (early Eocene respectively—post-Alveolina oblonga zone) cover the non-sulfidic Zn–(Pb) mineralization at temperatures as high as 60°C which is transitional from hypogene into supergene mineralization (“epithermal calamine deposits”). Stage 8 represents alteration of the pre-existing mineral assemblages in course of the Holocene weathering. The Cretaceous through Paleogene aquatic system is characterized by a poisoning of the sea with base metals, mainly Zn, and the atmosphere was chocked with clouds of fine-grained volcanic ejecta. Both processes contributed to the build-up of Zn–(Pb) deposits and vast, but uneconomic bentonitic clay deposits around the K/P boundary. Ore mineralization in the El Kef area is a multiple-phase process which reached its climax during the early Eocene as indicated by the large foram zones. These inorganic concentration processes resulting in the formation of mineral deposits had obviously also a negative effect on the long-term course of regional Earth’s biological history during the late Cretaceous–early Eocene period with lethal consequences for some species. The joint studies of inorganic and organic data reveal that such extraordinary metallogenetic processes close to the K/P boundary in its stratotype area in Tunisia were “strictly terrestrial”.     

Hydrochemical and isotopic properties of the Mahmutlu and Bağdatoğlu mineralized thermal springs, Kırşehir, Turkey

The present study identifies the hydrochemical and isotopic properties of the Mahmutlu and Ba?dato?lu mineralized thermal springs in K?r?ehir province, a geothermal field in central Anatolia, Turkey. Based on these properties, a hydrogeological regime is proposed in order to explain the Mahmutlu–Ba?dato?lu geothermal system. The relation between the concentrations of the environmental stable isotopes deuterium and oxygen-18 in the water is similar to the relationship in global meteoric water, indicating that the water is of meteoric origin. Evaluation of the geochemical characteristics of the water reveals that these two thermal springs belong to the same hydrogeological system. The hydrogeological system comprises a fractured limestone member of the Çevirme Formation and the Kervansaray Formation as reservoir rocks, and the Delice?rmak Formation as an overlying aquitard. The waters of the Mahmutlu and Ba?dato?lu springs are mainly of the Na-Cl-SO4 type that originate from the Pohrenk evaporite. The thermal waters are undersaturated with respect to calcite, dolomite, halite, and gypsum. The δ 18O and δ 2H contents indicate a δ 18O shift in the Mahmutlu and Ba?dato?lu waters. The temperature range of the two reservoirs is estimated to be 98–158?°C, on the basis of Na+K+Ca and SiO2 geothermometers.     

胂赴镅?美国 Ba

ylor College of Medicine癌症中心,美国转化生长因子β(TGF-β);;SMADs;;去磷酸化在后生动物机体中,转化生长因子β(TGF-β)及相关生长因子可以通过自分泌、旁分泌及内分泌方式影响广泛的生理活动。它们在?Quaternary Geology,ISSN0256-1492,CN37-1117/P,28(4),2006,p.29-35,5 illus.,13 refs.,with English abstract)Key words:land subsidence,Yellow River Delta     

胶东半岛三佛山高Ba—Sr花岗岩成因

胶东半岛三佛山岩体是昆嵛山杂岩体的重要组成部分，其岩性主要由二长花岗岩组成，位于苏鲁超高压碰撞带与胶东陆块之间的缝合带中。岩石化学特点具高钾钙碱性岩石系列特征，岩体为准铝Ⅰ型花岗岩，并具有高Ba—Sr花岗岩的岩石地球化学特征，即高Ba、Sr含量，高Sr／Y、La／Yb、K／Rb值，低Y（〈13μg／g）、Yb（1．8μg／g）、Rb／Sr比值（平均为0．33），弱的Eu负异常，亏损Nb、P、Ti等高场强元素。根据该岩体岩石地球化学特征、包体岩石学特征，并结合前人对高Ba—sr花岗岩成因研究成果，笔者认为该岩体可能是幔源基性岩浆与地壳熔融的酸性端元混合而成。混合后的岩浆没有明显的长石和云母类矿物的结晶分异作用，混合岩浆最大温度在750-800℃左右。酸性岩浆的源区以石榴子石＋辉石＋角闪石＋斜长石的残留为特征。残留相物质组成特征暗示源区应位于壳幔边界，深度30km土，结合早期形成的昆嵛山二长花岗岩源区深度大于40km这一现象，表明胶东地区中生代岩石圈减薄作用在110Ma达到最大，地壳厚度恢复至正常厚度。     

松辽盆地北部Sr、Ba异常与油田关系

初次进行甚低密度表层土壤测量结果表明,用Sr、Ba、U和放射性同位素~(210)Po作为油田的地表地球化学标志,能够圈定大部分油田位置,并能为整个盆地提出初步的评价意义。本文主要介绍松辽盆地北部120000km~2范围内的Sr、Ba正异常,U,~(210)Po的负异常与油田的关系。     

Imaging and analyzing rock porosity by autoradiography and Hg-porosimetry/X-ray computertomography—Applications

The application of two sets of methods for the characterization of rock pore systems is reported. Both are discussed in the context of other techniques described in the literature. (i) Impregnation with labelled polymethylmethacrylate (PMMA) and autoradiography or direct measurement of the tracer activity allows the investigation of the pattern of the spatial porosity distribution and quantitative measurement of mineral-specific, local porosities, porosity gradients as well as an assessment of hydraulic and diffusive transport properties. (ii) Quantitative information on surface areas within certain pore size ranges can be achieved by combination of mercury intrusion porosimetry with X-ray absorption computer-tomography. As examples of applications of these techniques, the effects of weathering, alteration, mechanical stress and large diameter coring on the pore network of rocks have been studied.     

Experimental Study of REEs,Ba, and Sr Interphase Partitioning in Fluid–Magmatic Silicate Systems at T = 1250°C and P = 2 kbar

The results of study of the alkaline silicate melt–hydrous saline (carbonate, sulfate, and fluoride) fluid system, as well as partitioning of ore metals (Ba, Sr, and REEs) between coexisting phases at T = 1250°C and P = 2 kbar are reported. It is shown that aqueous solutions with the compositions studied cannot be effective concentrators and transporters of ore elements such as REEs, Sr, and Ba. The sulfate melt accumulates Sr and Ba in the alkaline silicate melt–hydrous sulfate fluid system, which provides evidence for the efficiency of sulfate ore extraction of Sr and Ba from the melt. The results obtained support the important oregenerating role of dense saline phases formed upon the development of liquid heterogeneity in fluid–magmatic systems.

     

Patterns and implications of plant-soil δC and δN values in African savanna ecosystems

Southern African savannas are mixed plant communities where C₃ trees co-exist with C₄ grasses. Here foliar δ¹⁵N and δ¹³C were used as indicators of nitrogen uptake and of water use efficiency to investigate the effect of the rainfall regime on the use of nitrogen and water by herbaceous and woody plants in both dry and wet seasons. Foliar δ¹⁵N increased as aridity rose for both C₃ and C₄ plants for both seasons, although the magnitude of the increase was different for C₃ and C₄ plants and for two seasons. Soil δ¹⁵N also significantly increased with aridity. Foliar δ¹³C increased with aridity for C₃ plants in the wet season but not in the dry season, whereas in C₄ plants the relationship was more complex and non-linear. The consistently higher foliar δ¹⁵N for C₃ plants suggests that C₄ plants may be a superior competitor for nitrogen. The different foliar δ¹³C relationships with rainfall may indicate that the C₃ plants have an advantage when competing for water resources. The differences in water and nitrogen use likely collectively contribute to the tree-grass coexistence in savannas. Such differences facilitate interpretations of palaeo-vegetation composition variations and help predictions of vegetation composition changes under future climatic scenarios.     

Response of the coccolithophores Emiliania huxleyi and Coccolithus braarudii to changing seawater Mg and Ca concentrations: Mg/Ca, Sr/Ca ratios and δCa, δMg of coccolith calcite

Calcium and magnesium concentrations in seawater have varied over geological time scales. On short time scales, variations in the major ion composition of seawater influences coccolithophorid physiology and the chemistry of biogenically produced coccoliths. Validation of those changes via controlled laboratory experiments is a crucial step in applying coccolithophorid based paleoproxies for the reconstruction of past environmental conditions. Therefore, we examined the response of two species of coccolithophores, Emiliania huxleyi and Coccolithus braarudii, to changes in the seawater Mg/Ca ratio (≈0.5 to 10 mol/mol) by either manipulating the magnesium or calcium concentration under controlled laboratory conditions. Concurrently, seawater Sr/Ca ratios were also modified (≈2 to 40 mmol/mol), while keeping salinity constant at 35. The physiological response was monitored by measurements of the cell growth rate as well as the production rates of particulate inorganic and organic carbon, and chlorophyll a. Additionally, coccolithophorid calcite was analyzed for its elemental composition (Sr/Ca and Mg/Ca) as well as isotope fractionation of calcium and magnesium (Δ^44/40Ca and Δ^26/24Mg). Our results reveal that physiological rates were substantially influenced by changes in seawater calcium rather than magnesium concentration within the range estimated to have occurred over the past 250 million years when coccolithophores appear in the fossil record. All physiological rates of E. huxleyi decreased at a calcium concentration above 25 mmol L⁻¹, whereas C. braarudii displayed a higher tolerance to increased seawater calcium concentrations. Partition coefficient of Sr was calculated as 0.36 ± 0.04 (±2σ) independent of species. Partition coefficient of Mg²⁺ increased with increasing seawater Ca²⁺ concentrations in both coccolithophore species. Calcium isotope fractionation was constant at 1.1 ± 0.1‰ (±2σ) and not altered by changes in seawater Mg/Ca ratio. There is a well-defined inverse linear relationship between calcium isotope fractionation and partition coefficient of Sr²⁺ in all experiments, suggesting similar controls on both proxies in the investigated species. Magnesium isotope ratios were relatively stable for seawater Mg/Ca ratios ranging from 1 to 5, with a higher degree of fractionation in Emiliania huxleyi (by ≈0.2‰ in Δ^26/24Mg). Although Mg/Ca ratios in the calcite of coccolithophores and foraminifera are similar, the former have considerably higher Δ^26/24Mg (by >+3‰), presumably due to differences in calcification mechanisms between the two taxa. These observations suggest, a physiological control over magnesium elemental and isotopic fractionation during the process of calcification in coccolithophores.     

Generation of Muscovite/ Two-Mica Granil and Intracontinental Subduction

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