离子交换过程中锂同位素分馏对锂同位素测试准确度的影响

锂同位素被广泛应用于地球与行星科学各个领域,准确测定锂同位素比值是示踪各种自然过程的前提,但目前国际实验室报道的锂同位素标准物质测定值存在较大偏差,例如已报道的海水δ7Li测试值相差5‰。针对这一现状,本文基于离子交换理论基础,使用正态分布函数拟合淋出曲线,通过理论计算得到离子交换纯化过程造成的锂同位素分馏的理论值,该数值与MC-ICP-MS检测无关,但对锂同位素测试准确度有直接的影响。在此基础上,定义相对回收率(Rc)用于监测锂同位素分馏。基于本实验室分离纯化流程,通过理论计算得出,当Rc 99. 8%时,可认为离子交换纯化过程中没有引起可观察到的锂同位素分馏,进而不影响MC-ICP-MS检测准确度。目前世界上各实验室主要通过绝对回收率或Rc来判断分离过程中是否发生同位素分馏。由于测试的空间电荷效应,绝对回收率易被高估,而 99%的Rc并未全部达到理论计算得到的Rc,表明各实验室对同种标准物质测试结果的偏差极可能是由于离子交换纯化过程中锂同位素分馏导致的。本文提出,对于每一样品,只需要分别测量离子交换过程中接收区间及其前后一定区间溶液中锂含量,将得到的Rc值与其理论值比较,即可判断分离纯化过程中是否引起可观察到的锂同位素分馏。     

水体蒸发过程中稳定同位素分馏的模拟

通过对非平衡条件下水体蒸发中稳定同位素分馏机制的分析, 模拟了蒸发水体中稳定同位素比率的变化及与温度、大气湿度的关系. 在瑞利模式中, 剩余水中的稳定同位素随剩余水比例f的减小不断富集, 富集的速率与温度呈反比. 在动力蒸发条件下, 稳定同位素的分馏不仅与相变温度有关, 而且受大气湿度和液-气相之间物质交换的影响. 在动力蒸发过程中, 相对湿度越小, 剩余水中稳定同位素比率随 f的变化越快. 当相对湿度较大时, 在经历了一段时间蒸发后的剩余水中的δ将不随 f变化. 蒸发水体达到稳定状态的速率主要取决于大气的相对湿度. 当温度约20℃时, 在瑞利平衡条件下模拟的蒸发线与全球大气水线较接近. 在非平衡蒸发条件下, 蒸发线的梯度项和常数项与温度和相对湿度呈正比.     

低温环境下Zn同位素分馏的若干重要过程

锌同位素是一种新的地球化学示踪剂,详细了解锌同位素分馏过程与机理是运用其解决科学问题的关键.本文对前人研究的吸附、沉淀、扩散、还原、生物过程中的锌同位素分馏研究结果进行了系统总结.在沉淀过程中.沉淀富集轻同位素;随着扩散距离增加,溶液Zn同位素组成变轻;还原生成的金属Zn富集轻同位素;在生物参与的Zn地球化学循环过程中,硅藻表面吸附重同位素,但生物本身优先利用轻同位素.     

热扩散过程中硅酸盐熔体的同位素分馏机制

1研究背景Soret效应是指在热梯度作用下,处于化学平衡状态的液相系统中某些组分自发产生浓度梯度的过程,也称为热扩散,这一现象首先由德国科学家Ludwig(1856)预言,被瑞士科学家Soret(1879)实验所证实,所以也叫Ludwig-Soret效应。实验已经证明,在有温度梯度存在     

地质样品铊同位素分析预处理方法优化

铊同位素体系可以示踪天体演化、古环境变化、矿床成因及污染物迁移等地质过程。然而,目前用于铊同位素分析的样品消解和离子交换方法耗时较长,往往需要两周甚至更久;为了提高化学前处理效率,本文采用微波消解法分解样品,以AG1-X8阴离子交换树脂纯化铊,采用多接收器电感耦合等离子体质谱(MC-ICP-MS)测试,仪器的质量歧视用铅同位素标准溶液(NIST SRM981)校正。通过考察消解条件、淋洗曲线和基质效应,结果表明:采用微波消解法,在2mL硝酸-2mL氢氟酸-0.5mL高氯酸的混合酸体系中选用适当的消解程序可以将0.2g土壤标准物质GBW07406消解完全,总耗时不超过2h;利用AG1-X8树脂,上样后,依次以2mL 2mol/L硝酸-1%溴水淋洗6次、2mL超纯水淋洗1次和2mL 0.1mol/L盐酸-6%二氧化硫淋洗5次(收集铊),可有效地纯化铊;常见共存元素的干扰实验结果显示,树脂填充量为2mL时,该淋洗流程所允许上样溶液中含有三价铁和三价铝离子的量分别不应超过2.56mmol和4.90mmol,否则会使铊的回收率降低。将此方法应用于4个地质标准物质中铊同位素比值的测定,ε^...     

低温环境下铁同位素分馏的若干重要过程

详细了解同位素分馏的过程与机理是运用稳定同位素体系解决科学问题的关键.本文对沉淀、溶解、吸附、氧化、还原、生物等过程中的Fe同位素分馏研究结果进行了系统总结.在沉淀过程中,优先沉淀轻同位素;在吸附过程中,Fe(Ⅲ)矿物优先吸附重同位素;氧化还原过程中,Fe的化合价越高,Fe同位素组成越重.     

AG-MP-1M阴离子交换树脂分离-表面热电质谱法测定沉积物中的铅同位素组成

利用新型阴离子交换树脂分离沉积物中的重金属Pb,采用表面热电离质谱法(TIMS)测定了沉积物样品中的Pb同位素组成。新型树脂为大孔径阴离子树脂AG-MP-1M,淋洗液采用低浓度的盐酸,避免了使用难以纯化的氢溴酸,可有效地降低试剂空白。通过对铅同位素标准物质NIST NBS-981的重复测试,方法的精密度(<0.5%,2s)和准确度均达到了应用研究的要求。对5个实际沉积物样品中的铅同位素组成进行测定,获得了理想的分析效果。     

低温环境下铜同位素分馏的若干重要过程

Cu同位素是一种新的地球化学示踪剂.正确运用这一同位素示踪技术的前提是对其同位素分馏机理和过程有足够的认识.本文报道了室温下CuSO4·5H2O结晶过程产生分馏的实验结果,并系统地总结了低温条件下Cu同位素分馏的一些重要过程,其中包括沉淀过程、还原过程、吸附过程、生物过程等.     

柱色谱分离-分子筛络合洗脱过程中正构烷烃单体碳同位素分馏研究

应用气相色谱-气体同位素质谱（GC-C-IRMS）分析正构烷烃单体碳同位素之前,需要对饱和烃样品中正构烷烃和异构烷烃进行预分离、富集,在预分离和富集过程中正构烷烃单体碳同位素是否发生分馏是高精度分析正构烷烃单体碳同位素比值（δ13C）的关键。本文以正构烷烃混合溶液为对象,利用柱色谱、5Å分子筛络合、环己烷-正戊烷混合溶剂两次洗脱,GC-C-IRMS分析正构烷烃单体碳同位素,研究前处理过程中正构烷烃单体碳同位素是否发生分馏。结果表明：使用柱色谱分离前后,多数正构烷烃单体碳同位素比值相差-0.2‰~0.2‰;当5Å分子筛不完全络合时,未络合的正构烷烃单体碳同位素比值偏重约0.7‰,可能发生了微弱的碳同位素分馏,但并未影响洗脱后的正构烷烃单体碳同位素比值;使用环己烷-正戊烷混合溶剂洗脱前后,碳同位素比值相差-0.2‰~0.5‰,以同样方式洗脱第二次,获得的正构烷烃单体碳同位素比值与模拟样品相差-0.3‰~0.2‰。分析不同回收率（>20%）正构烷烃的单体碳同位素比值,处理前后的差值基本在0.3‰以内,可见当正构烷烃回收率低至20%左右时,其单体碳同位素仍未发生明显分馏。柱色谱分离-5Å分子筛络合-混合溶剂洗脱方法适用于回收率大于20%的正构烷烃单体碳同位素分析。     

用于多接收器等离子体质谱铜铁锌同位素测定的离子交换分离方法

采用AGMP-1阴离子交换树脂，分别以7mol／L HCl、2mol／L HCl、0．5mol／L HNO3作为淋洗剂，可有效分离Cu、Fe、Zn。介绍了方法的基本原理、化学分离过程及混合标准溶液与地质标样的分离结果。结果表明，Cu、Fe、Zn回收率均接近100％，标准溶液在离子交换分离前后同位素组成一致，可以满足多接收器等离子体质谱对Cu、Fe、Zn同位素高精度分析的要求。     

AG MP-1M阴离子分离Cu、Fe、Zn及其在Fe同位素测定上的应用

采用新型阴离子交换树脂AG MP-1M,分别以8.2 mol/L HCl+0.01%HF、4 mol/L HCl、2 mol/L HCI和0.5 mol/L HNO,可以有效分离地质样品中Cu、Co、Fe和Zn,克服了AG MP-1阴离子交换树脂分离Cu时Co随Cu同时淋洗下来,以及在分离Co含量较高的地质样品时Co和Cu需过二次柱分离的弊端.对花岗闪长岩等地质标样的研究结果表明,AG MP-1M阴离子交换树脂能有效分离Cu、Fe和Zn,并且它们的回收率均大于99%.标准样品经过离子交换分离后Fe同位素未发生分馏,可满足多接收器电感耦合等离子体质谱(MC-ICPMS)的同位素测定要求.     

Separation of Heavy Lanthanoids by Flash Column Chromatography for Precise Determination of Er and Yb Isotope Compositions in Rock Samples

We present a new column chemistry technique for the quantitative separation of heavy lanthanoids by an ultra‐fine‐grained LN resin (20–50 µm) with a specific emphasis on the purification of Er and Yb for their isotopic analysis. To achieve the quantitative separation of Er and Yb within a reasonable timescale, flash column chromatography was applied, where the column was attached to a newly designed vacuum box system, thus accelerating the elution speed by ten times compared with that of the normal column procedure operated by gravity flow. The recovery yields of Er and Yb were confirmed to be approximately 100%, which is important to suppress the effect of the mass‐independent fractionation of the Er and Yb isotopes during chromatography. Additionally, we have developed precise Er and Yb isotope measurements by thermal ionisation mass spectrometry (TIMS) using multistatic and/or dynamic methods. Moreover, in most cases, the Er and Yb isotope compositions of the measured four terrestrial rock samples were indistinguishable from those of the commercially available Er and Yb Alfa Aesar solutions. The new method presented in this work will be useful for future studies on heavy lanthanoids in various geological materials.     

生物气CO2还原途径中碳同位素分馏作用研究及应用

地质历史中,CO2/H2还原产甲烷作用对生物气的形成具有十分重要的意义。中国柴达木盆地第四系生物气主要为CO2/H2还原型生物气。笔者以CO2/H2还原生气理论为指导,进行不同初始碳同位素值和不同赋存状态碳源的生物模拟实验,研究CO2/H2还原产气过程中发生的碳同位素分馏作用。实验结果表明,产物中δ13CH4值与底物的δ13C值呈很好的正相关关系;在反应母质过量的情况下,碳源的赋存状态可以影响产物甲烷的碳同位素组成。以游离形式CO2还原产生的甲烷δ13C值,相对于以HCO3-、CO23-离子形式产生的甲烷δ13C值轻。通过柴达木盆地东部第四系生物气田实例分析,探讨了该区生物气的主要底物CO2的来源及赋存状态,对评价盆地生物气资源和有利勘探区预测有重要的参考价值。     

Crustal-scale magmatic systems during intracontinental strike-slip tectonics: U, Pb and Hf isotopic constraints from Permian magmatic rocks of the Southern Alps

The Southern Alps host volcano-sedimentary basins that formed during post-Variscan extension and strike-slip in the Early Permian. We present U–Pb ages and initial Hf isotopic compositions of magmatic zircons from silicic tuffs and pyroclastic flows within these basins, from caldera fillings and from shallow intrusions from a 250 km long E–W transect (Bozen–Lugano–Lago Maggiore) and compare these with previously published data. Basin formation and magmatism are closely related to each other and occurred during a short time span between 285 and 275 Ma. The silicic magmatism is coeval with mafic intrusions of the Ivrea-Verbano Zone and within Austroalpine units. We conclude that deep magma generation, hybridisation and upper crustal emplacement occurred contemporaneously along the entire transect of the Southern Alps. The heat advection in the lower crust by injected mantle melts was sufficient to produce crustal partial melts in lower crustal levels. The resulting granitoid melts intruded into the upper crust or rose to the surface forming large caldera complexes. The compilation of Sr and Nd isotopic data of these rocks demonstrates that the mantle mixing endmember in the melts may not be geochemically enriched but has a depleted composition, comparable to the Adriatic subcontinental mantle exhumed to form the Tethyan sea floor during Mesozoic continental breakup and seafloor spreading. Magmatism and clastic sedimentation in the intracontinental basins was interrupted at 275 Ma for some 10–15 million years, forming a Middle Permian unconformity. This unconformity may have originated during large-scale strike-slip tectonics and erosion that was associated with crustal thinning, upwelling and partial melting of mantle, and advection of melts and heat into the crust. The unconformity indeed corresponds in time to the transition from a Pangea-B plate reconstruction for the Early Permian to the Late Permian Pangea-A plate assembly (Muttoni et al. in Earth Planet Sci Lett 215:379–394, 2003). The magmatic activity would therefore indicate the onset of >2,000 km of strike-slip movement along a continental-scale mega-shear, as their model suggests.     

Elemental and Sr–Nd–Pb isotopic geochemistry of Late Paleozoic volcanic rocks beneath the Junggar basin, NW China: Implications for the formation and evolution of the basin basement

The basement beneath the Junggar basin has been interpreted either as a micro-continent of Precambrian age or as a fragment of Paleozoic oceanic crust. Elemental and Sr–Nd–Pb isotopic compositions and zircon Pb–Pb ages of volcanic rocks from drill cores through the paleo-weathered crust show that the basement is composed mainly of late Paleozoic volcanic rock with minor shale and tuff. The volcanic rocks are mostly subalkaline with some minor low-K rocks in the western Kexia area. Some alkaline lavas occur in the central Luliang uplift and northeastern Wulungu depression. The lavas range in composition from basalts to rhyolites and fractional crystallization played an important role in magma evolution. Except for a few samples from Kexia, the basalts have low La/Nb (<1.4), typical for oceanic crust derived from asthenospheric melts. Zircon Pb–Pb ages indicate that the Kexia andesite, with a volcanic arc affinity, formed in the early Carboniferous (345 Ma), whereas the Luliang rhyolite and the Wucaiwan dacite, with syn-collisional to within-plate affinities, formed in the early Devonian (395 and 405 Ma, respectively). Positive ε_Nd(t) values (up to +7.4) and low initial ⁸⁷Sr/⁸⁶Sr isotopic ratios of the intermediate-silicic rocks suggest that the entire Junggar terrain may be underlain by oceanic crust, an interpretation consistent with the juvenile isotopic signatures of many granitoid plutons in other parts of the Central Asia Orogenic Belt. Variation in zircon ages for the silicic rocks, different Ba, P, Ti, Nb or Th anomalies in the mafic rocks, and variable Nb/Y and La/Nb ratios across the basin, suggest that the basement is compositionally heterogeneous. The heterogeneity is believed to reflect amalgamation of different oceanic blocks representing either different evolution stages within a single terrane or possibly derivation from different terranes.     

Lu–Hf and U–Pb isotope systematics of zircons from the Storgangen intrusion, Rogaland Intrusive Complex, SW Norway: implications for the composition and evolution of Precambrian lower crust in the Baltic Shield

The Storgangen orebody is a concordantly layered, sill-like body of ilmenite-rich norite, intruding anorthosites of the Rogaland Intrusive Complex (RIC), SW Norway. 17 zircon grains were separated from ca. 5 kg of sand-size flotation waste collected from the on-site repository from ilmenite mining. These zircons were analysed for major and trace elements by electron microprobe, and for U–Pb and Lu–Hf isotopes by laser ablation microprobe plasma source mass spectrometry. Eight of the zircons define a well-constrained (MSWD=0.37) concordant population with an age of 949±7 Ma, which is significantly older than the 920–930 Ma ages previously reported for zircon inclusions in orthopyroxene megacrysts from the RIC. The remaining zircons, interpreted as inherited grains, show a range of ²⁰⁷Pb/²⁰⁶Pb ages up to 1407±14 Ma, with an upper intercept age at ca. 1520 Ma. The concordant zircons have similar trace element patterns, and a mean initial Hf isotope composition of ¹⁷⁶Hf/¹⁷⁷Hf_{949 Ma}=0.28223±5 (_Hf=+2±2). This is similar to the Hf-isotope composition of zircons in a range of post-tectonic Sveconorwegian granites from South Norway, and slightly more radiogenic than expected for mid-Proterozoic juvenile crust. The older, inherited zircons show Lu–Hf crustal residence ages in the range 1.85–2.04 Ga. One (undated) zircon plots well within the field of Hf isotope evolution of Paleoproterozoic rocks of the Baltic Shield. These findings indicate the presence of Paleoproterozoic components in the deep crust of the Rogaland area, but do not demonstrate that such rocks, or a Sveconorwegian mantle-derived component, contributed significantly to the petrogenesis of the RIC. If the parent magma was derived from a homogeneous, lower crustal mafic granulite source, the lower crustal protolith must be at least 1.5 Ga old, and it must have an elevated Rb/Sr ratio. This component would be indistinguishable in Sr, Nd and Hf isotopes from some intermediate mixtures between Sveconorwegian mantle and Paleoprotoerzoic felsic crust, but it cannot account for the initial ¹⁴³Nd/¹⁴⁴Nd of the most primitive, late Sveconorwegian granite in the region, without the addition of mantle-derived material.     

Climate and environment during the Younger Dryas (GS‐1) as reflected by composite stable isotope records of lacustrine carbonates at Torreberga,southern Sweden

Climatic and environmental changes during the Younger Dryas stadial (GS‐1) and preceding and following transitions are inferred from stable carbon and oxygen isotope records obtained from the sediments of ancient Lake Torreberga, southern Sweden. Event GS‐1 is represented in the sediment sequence by 3.5 m of clay containing lacustrine carbonates of various origins. Comparison of isotopic records obtained on mollusc shells, ostracod valves, and Chara encrustations precipitated during specific seasons of the year supports estimates of relative changes in both lake water and mean annual air temperatures. Variations in soil erosion rates can also be estimated from a simple isotope–mass‐balance model to separate allochthonous and autochthonous carbonate contributions to the bulk carbonate content of the sediments. The well‐known, rapid climatic shifts characterising the Last Termination in the North Atlantic region are clearly reflected in the isotopic data, as well as longer‐term changes within GS‐1. Following maximum cooling shortly after the Allerød–Younger Dryas (GI‐1–GS‐1) transition, a progressive warming and a slight increase in aquatic productivity is indicated. At the Younger Dryas–Preboreal (GS‐1–PB) transition mean annual air temperature rapidly increased by more than 5°C and summer lake‐water temperature increased by ca. 12°C. The subsequent Preboreal oscillation is characterised by an increase in soil erosion and a slight decrease in mean annual air temperature. These results are in harmony with recent findings about large‐scale climate dynamics during the Last Termination. Copyright © 1999 John Wiley & Sons, Ltd.     

History of crustal growth and recycling at the Pacific convergent margin of South America at latitudes 29°–36° S revealed by a U–Pb and Lu–Hf isotope study of detrital zircon from late Paleozoic accretionary systems

Detrital zircon provides a powerful archive of continental growth and recycling processes. We have tested this by a combined laser ablation ICP-MS U–Pb and Lu–Hf analysis of homogeneous growth domains in detrital zircon from late Paleozoic coastal accretionary systems in central Chile and the collisional Guarguaráz Complex in W Argentina. Because detritus from a large part of W Gondwana is present here, the data delineate the crustal evolution of southern South America at its Paleopacific margin, consistent with known data in the source regions.Zircon in the Guarguaráz Complex mainly displays an U–Pb age cluster at 0.93–1.46 Ga, similar to zircon in sediments of the adjacent allochthonous Cuyania Terrane. By contrast, zircon from the coastal accretionary systems shows a mixed provenance: Age clusters at 363–722 Ma are typical for zircon grown during the Braziliano, Pampean, Famatinian and post-Famatinian orogenic episodes east of Cuyania. An age spectrum at 1.00–1.39 Ga is interpreted as a mixture of zircon from Cuyania and several sources further east. Minor age clusters between 1.46 and 3.20 Ga suggest recycling of material from cratons within W Gondwana.The youngest age cluster (294–346 Ma) in the coastal accretionary prisms reflects a so far unknown local magmatic event, also represented by rhyolite and leucogranite pebbles. It sets time marks for the accretion history: Maximum depositional ages of most accreted metasediments are Middle to Upper Carboniferous. A change of the accretion mode occurred before 308 Ma, when also a concomitant retrowedge basin formed.Initial Hf-isotope compositions reveal at least three juvenile crust-forming periods in southern South America characterised by three major periods of juvenile magma production at 2.7–3.4 Ga, 1.9–2.3 Ga and 0.8–1.5 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf of Mesoproterozoic zircon from the coastal accretionary systems is consistent with extensive crustal recycling and addition of some juvenile, mantle-derived magma, while that of zircon from the Guarguaráz Complex has a largely juvenile crustal signature. Zircon with Pampean, Famatinian and Braziliano ages (< 660 Ma) originated from recycled crust of variable age, which is, however, mainly Mesoproterozoic. By contrast, the Carboniferous magmatic event shows less variable and more radiogenic ¹⁷⁶Hf/¹⁷⁷Hf, pointing to a mean early Neoproterozoic crustal residence. This zircon is unlikely to have crystallized from melts of metasediments of the accretionary systems, but probably derived from a more juvenile crust in their backstop system.