洋壳蚀变过程中Cu和Zn同位素分馏:对海洋Cu和Zn循环的制约

<正>铜(Cu)和锌(Zn)属于第一过渡族金属元素,分别有2种(63Cu、65Cu)和5种(64Zn、66Zn、67Zn、68Zn、70Zn)稳定同位素。Cu-Zn都属于生命元素,它们在海洋中的地球化学循环对海洋生产率发挥着重要作用。现有研究表明,海水的δ65Cu和δ66Zn分别为ca.0.9‰和ca.0.5‰,显著重于河水的Cu-Zn同位素组成(δ65Cu=ca.0.6‰和δ66Zn=ca.0.3‰);说明海洋中至少存在一个具有轻Cu-Zn同位素组成的储库。海底Fe-Mn结壳和碳酸盐岩石海洋Cu-Zn输出的重要渠道。已有研究表明,三大洋中的Fe-Mn结壳的δ65Cu和δ66Zn分别为0.44±0.23‰和1.04     

MC-ICP-MS高精度Cu、Zn同位素测试技术

过渡族元素同位素是国际上同位素地球化学研究的热点。测试技术的限制是制约过渡元素同位素研究发展的关键。笔者利用Neptune型多接收等离子质谱(MC-ICP-MS),采用Cu、Zn互为内标的方法对仪器的质量歧视进行了校正,对基质效应和测试方法的重现性进行了检验,建立了高精度的Cu、Zn同位素测试技术。在5个月内对实验室标准IMRCu和IMRZn进行了测量,结果分别为δ65CuNIST976=(0.34±0.08)‰(2SD,n=32),δ66ZnJMCZn=(-9.64±0.05)‰(2SD,n=26),δ67ZnJMCZn=(-14.37±0.16)‰(2SD,n=26),δ68ZnJMCZn=(-19.01±0.08)‰(2SD,n=26),分析精度达到国际同类实验室先进水平。对Cu、Zn同位素参考物质进行了对比测量,分析结果与报道值在误差范围内完全一致。     

多接收器等离子体质谱法Zn同位素比值的高精度测定

详细报道了Zn同位素比值的多接收器等离子体质谱(MC-ICP-MS)高精度测定方法,包括:MC-ICP-MS Zn同位素测量过程中的质量歧视校正、同质异位素干扰评估、基质效应调查和同位素测量的长期重现性检验.研究表明,在测定条件下,运用标样一样品交叉法能有效地进行仪器质量歧视校正.同质异位素干扰的评估通过3种方式进行,即:在高分辨状态下同质异位数干扰信号的直接测定,低分辨状态下Zn同位素原始数据间相关关系的检验和低分辨下浓度梯度效应研究.结果表明,在低分辨模式下,尽管66Zn、67Zn、68Zn的同质异位素干扰信号很小,但的确存在,要获得准确同位素比值,必须使标样和样品的浓度在合适的范围内匹配.在基质效应方面,主要考察Fe对Zn同位素比值测定的影响.结果表明,当溶液中Fe/Zn(质量比)不大于0.2时,Fe对Zn同位素比值测定无影响.重复性测定中,δ66ZnGSB-Romil=6.96‰±0.11‰(2sd),δ67ZnGSB-Romil=10.4‰±0.20‰(2sd),δ68ZnGSB-Romil=13.8‰±0.22‰(2sd),达到国际同类实验室先进水准.运用所建立的方法,对地质岩石成分分析国家标准物质GBW 07270(闪锌矿)进行了Zn同位素平均成分测定为:δ66Zn=6.71‰±0.03‰(20),δ67Zn=10.08‰±0.05‰(20),δ68Zn=13.37‰±0.07‰(2σ).     

海洋沉积物的铁和锌同位素测定

介绍海洋沉积物Fe和Zn同位素化学前处理及测定方法,报道南海西部夏季上升流区两个沉积物柱样的Fe和Zn同位素组成。样品采用HF+HNO3+HClO4常压消解,经脱盐后,转化为氯化物形式并经离子交换柱分离纯化后,用多接收器等离子体质谱法测定Fe和Zn同位素比值。该前处理方法可以快捷地实现海洋沉积物的消解、有机质的去除和海盐脱离;结合相关测试流程,可获得较高的δ56Fe(0.10‰,2SD)和δ66Zn分析精度(0.11‰,2SD)。两个沉积物柱样的δ56Fe值(相对于IRMM-014)和δ66Zn值(相对于JMC3-0749C)随深度变化不明显,两柱之间也无明显差异。总体上,南海西部上升流区1～2 ka以来的沉积物δ56Fe值(0.04‰～0.20‰)和δ66Zn值(0.12‰～0.30‰)与已报道的黄土和气溶胶、火成岩以及大部分海洋沉积物接近,明显高于静海相海洋沉积物的δ56Fe值。     

Zinc isotopic behavior of mafic rocks during continental deep subduction

Zinc isotopes may act as a new tool of tracking recycling of crustal materials that causes compositional heterogeneity of the mantle.This application relies on an investigation of Zn isotopic behaviors during slab subduction.In this study,we re port Zn isotopic compositions for a suite of metabasalts(greenschists,amphibolite s,and coesitebearing eclogites) from the Dabie Orogen(China),which were formed via the subduction of mafic rocks into different depths and up to 200 km.Three out of eight greenschists are characterized by lighter δ~(66)Zn_(JMC-Lyon)(0.10‰-0.16‰) than those of global basalts(0.28‰± 0.05‰),which may be caused by crustal assimilation of the protoliths by sedimentary rocks due to their extremely high ~(87)Sr/~(86)Sr(up to 0.7130) and low sNd values(down to-12.3).The remaining greenschists have relatively low ~(87)Sr/~(86)Sr and their δ~(66)Zn values(0.21‰-0.38‰) overlap the ranges of amphibolites(0.18‰-0.32‰) and coesite-bearing eclogites(0.18‰-0.36‰).There is no correlation between δ~(66)Zn and sensitive indicators of dehydration(Rb/TiO_2 Ba/Yb, and H_2 O~+), suggesting that no detectable Zn isotope fractionation has occurred during the deep subduction of mafic rocks even into 200 km,which is attributed to the limited loss of Zn during prograde metamorphism and dehydration.Thus,Zn isotopic compositions of the deeply subducted mafic rocks are inherited from their protoliths.Considering that these metamorphosed rocks have higher δ~(66)Zn than that of the mantle value by up to 0.2‰, the recycled/subducted mafic crust can incorporate isotopically heavy Zn into the mantle.The subducted slabs may partially melt and generate a metasomatized mantle,resulting in changes of Zn isotopic composition of the hybridized mantle as have been observed in some mantle xenoliths and ba saltic lavas.     

玄武岩标准样品铁铜锌同位素组成

报道了三种玄武岩标准样品(BCR-2、BIR-1a和GBW 07105)的铁铜锌同位素数据。实验使用HNO3-HF混合酸消解玄武岩标准样品;AGMP-1阴离子交换树脂分离提纯样品中的铜铁锌,利用多接收等离子体质谱仪(MC-ICPMS)测定铁铜锌同位素比值,分析过程中使用样品-标准-样品交叉法校正仪器的质量分馏。实验得到BCR-2、BIR-1a和GBW 07105标准样品的高精度铁铜锌同位素组成(95%置信水平的不确定度)分别为:δ56FeBCR-2-IRMM014=0.070‰±0.018‰(2SD),δ65 CuBCR-2-SRM976=0.16‰±0.04‰(2SD),δ66 ZnBCR-2-IRMM3702=-0.072‰±0.020‰(2SD);δ56 FeBIR-1a-IRMM014=0.044‰±0.026‰(2SD),δ65CuBIR-1a-SRM976=0.027‰±0.019‰(2SD),δ66 ZnBIR-1a-IRMM3702=0.085‰±0.032‰(2SD);δ56FeGBW 07105-IRMM014=0.126‰±0.039‰(2SD),δ65 CuGBW 07105-SRM976=0.12‰±0.01‰(2SD),δ66ZnGBW 07105-IRMM3702=0.22‰±0.03‰(2SD)。这些数据在误差(不确定度)范围内与国际上已发表的数据是一致的。三个玄武岩标准样品的铁铜锌同位素组成数据的发表为铁铜锌同位素研究提供了统一的标准,使地质样品的铁铜锌同位素数据的质量监控成为可能。     

喀斯特高原湖泊生物地球化学过程中的锌同位素特征

采用多接收电感耦合等离子体质谱仪(MC-ICP-MS)对喀斯特高原湖泊红枫湖、阿哈湖水体及其主要支流水体悬浮物和一些生物样品中的锌同位素进行了测定,测试精度小于0.11‰(2SD).结果显示,红枫湖水体与其主要支流水体悬浮物中的δ66Zn变化范围分别为-0.29‰～0.26‰和-0.04‰～0.48‰,阿哈湖水体与其主要支流水体悬浮物中的δ66Zn变化范围分别为-0.18‰～0.27‰和-0.179‰～0.46‰,均表现出支流中的锌同位素组成较重的特点.两湖生物样品中的δ66Zn变化范围较大,为-0.35‰～0.57‰,说明湖泊生态系统中各端员的锌同位素组成存在一定差异.根据同位素组成分析,湖泊主要入湖河流及所携带的陆源物质是阿哈湖泊水体中锌的主要来源,锌同位素是一种较好的物源示踪工具.红枫湖夏季δ66zn与Chla(叶绿素)呈显著的正相关(R=0.97),主要是藻类对锌的有机吸附和吸收过程导致锌同位素组成发生变化.此外,湖泊水体悬浮物中的锌同位素组成均在夏季较轻,表明大气的干湿沉降可能是一个较负的锌同位素源.水体悬浮物中的δ66Zn变化范围小于生物样品中的δ66Zn变化范围,说明由于生物作用过程导致的锌同位素分馏大于非生物过程.     

过渡族金属元素同位素分析方法及其地质应用

由于同位素分析方法的改进和多接收电感耦合等离子体质谱仪 (MC ICP MS)的应用 ,近年来过渡族金属元素 (Cu ,Zn和Fe)同位素地球化学有了长足进步 ,成为国际地学领域的一个前沿研究方向。Cu同位素在自然界中的变化最大 ,δ65Cu值为 - 3.70‰～ +2 .0 5‰ ;Zn和Fe同位素变化比Cu同位素变化小 ,δ66Zn值为 - 0 .6 4‰～ +1.16‰ ,而δ56Fe值为 - 1.6 2‰～ +0 .91‰。自然界中各种无机过程 (从高温到低温 )和生物有机过程均能使Cu ,Zn和Fe同位素发生分馏。Cu、Zn和Fe在自然界中广泛分布于各类矿物、岩石、流体和生物体中 ,并广泛参与成岩成矿作用、热液活动和生命活动过程。因此 ,这些过渡族金属元素同位素已在陨石和宇宙化学、矿床学 ,海洋学和生物学等领域的研究中取得了显著成效 ,并将成为地球科学中具有巨大应用前景的一种新的地球化学手段。     

贵州纳雍枝铅锌矿床成因研究：来自镉同位素和微量元素的约束

纳雍枝铅锌矿床是贵州省内发现的第一个大型铅锌矿床,前人对该矿床进行过大量地质和地球化学研究,对该矿床成因有了一定认识,但其成矿金属来源,特别是其中稀散金属(如Cd)的来源却少有涉及。本文分析了该矿床硫化物和精矿样品的微量元素及镉同位素组成,结合该区域不同地质端元的地球化学数据,来探讨以Cd为代表的稀散金属来源。结果表明,样品的Zn/Cd值变化较大(377～953),均高于川滇黔地区沉积岩的Zn/Cd比值(13～367),而更接近火成岩的Zn/Cd值(515～1319)。精矿和闪锌矿样品的镉同位素组成(δ^114/110Cd _NIST-3108)变化范围极小(-0.09‰～-0.05‰),与已获得的岩浆岩数据一致(-0.22‰～0.15‰),但明显区别于该地区的碳酸盐岩地层(-0.25‰～0.82‰)。结合精矿的Zn/Cd-δ^114/110Cd _NIST-3108关系图解和前人研究成果,本文认为该矿床金属成矿物质(如镉、铅等)主要来自基底。     

多接收器电感耦合等离子体质谱法测定土壤标准物质铜同位素组成

近年来,铜同位素在表生环境和生物地球化学中的应用越来越广泛,尤其是土壤的铜同位素组成可以示踪环境污染物来源及生物地球化学过程。目前,对土壤铜同位素进行研究时,主要以硅酸岩标准物质为标样来衡量土壤样品铜同位素测定的准确性和精确性。但土壤与硅酸岩中铜、基质离子及有机质的含量等存在很大差异(如:硅酸岩中的铜含量80μg/g,一些土壤中的铜含量很低,20μg/g),将硅酸岩标准物质作为标样来监测土壤样品的数据质量缺乏代表性。为了弥补这一缺陷,本文精确测定4个国家土壤标准物质(GBW07443、GBW07425、GBW07427、GBW07389)的铜同位素组成,并将其作为检验土壤样品铜同位素测定过程中的标准。实验中采用高温高压反应釜消解样品,利用AG MP-1M树脂进行纯化,全流程空白2ng,回收率≥98%,通过多接收器电感耦合等离子体质谱仪(MC-ICP-MS)采用标样-样品-标样间插法进行仪器分馏校正,δ~(65)Cu的长期测试外精度优于0.05‰(n=306, 2SD)。GBW07443、GBW07425、GBW07427和GBW07389的铜同位素组成分别为-0.04‰±0.04‰(n=9, 2SD)、-0.07‰±0.05‰(n=12, 2SD)、-0.06‰±0.04‰(n=12, 2SD)、-0.02‰±0.06‰(n=12, 2SD)。这些土壤标准物质的铜同位素组成均位于0附近,大致为自然界土壤铜同位素比值变化范围(-0.5‰～+0.5‰)的中间值,且样品容易获得,其化学和铜同位素组成均一,适合作为监控土壤铜同位素化学及质谱分析数据可靠性的标准物质。     

Inter-regional correlation of transgressions and regressions in the Cretaceous period

Well investigated platforms have been selected in each continent, and the history of Cretaceous transgressions and regressions there is concisely reviewed from the available evidence. The factual records have been summarized into a diagram and the timing of the events correlated between distant as well as adjoining areas.On a global scale, major transgressions were stepwise enlarged in space and time from the Neocomian, via Aptian-Albian, to the Late Cretaceous, and the post-Cretaceous regression was very remarkable. Minor cycles of transgression-regression were not always synchronous between different areas. Some of them were, however, nearly synchronous between the areas facing the same ocean.Tectono-eustasy may have been the main cause of the phenomena of transgression-regression, but certain kinds of other tectonic movements which affected even the so-called stable platforms were also responsible for the phenomena. The combined effects of various causes may have been unusual in the Cretaceous, since it was a period of global tectonic activity. The slowing down of this activity followed by readjustments may have been the cause of the global regression at the end of the Cretaceous.     

The lamprophyres of Afyon stratovolcano,western Anatolia,Turkey: description and genesis

The Afyon stratovolcano exhibits lamprophyric rocks, emplaced as hydrovolcanic products, aphanitic lava flows and dyke intrusions, during the final stages of volcanic activity. Most of the Afyon volcanics belong to the silica-saturated alkaline suite, as potassic trachyandesites and trachytes, while the products of the latest activity are lamproitic lamprophyres (jumillite, orendite, verite, fitztroyite) and alkaline lamprophyres (campto-sannaite, sannaite, hyalo-monchiquite, analcime–monchiquite). Afyon lamprophyres exhibit LILE and Zr enrichments, related to mantle metasomatism.     

NONMETALS DEPOSITS

正20140876 Gao Junbo(College of Resources and Environmental Engineering,Guizhou University,Guiyang 550025,China);Yang Ruidong Study on the Strontium Isotopic Composition of Large Devonian Barite Deposits from Zhenning,Guizhou Province(Geochimica,     

METALS DEPOSITS

正20141470 Chai Lu(Shenyang Institute of Geology and Mineral Resources,CGS,Shenyang110034,China);Zhu Qun Distribution of Significant Metal Mineral Resources the in Adjacent Areas of China,Russia and Mongolia(Geology and Resources,ISSN1671-1947,CN21-1458/P,22(5),2013,p.397-402,2 illus.,3 tables,20 refs.)Key words:metal ores,China,Russia,Mongolia     

GEOPHYSICS

正20141944Bao Hanyong(Research Institute of Exploration and Development,Jianghan Oilfield,SINOPEC,Wuhan 430223,China);Guo Zhanfeng Tectonic-Thermal Evolution of the Subei Basin since the Late Cretaceous(Geological Journal of China Universities,ISSN1006-7493,CN32-1440/P,19(4),     

GEOCHEMISTRY

正20140692 Duo Tianhui(No.402 Geological Team,Exploration of Geology and Mineral Resources of Sichuan Authority,Chengdu611730,China);Wang Yongli Computer Simulation of Neptunium Existing Forms in the Groundwater(Computing Techniques for Geophysical and Geochemical Exploration,ISSN1001-1749,CN51-1242/P,35(3),     

ENVIRONMENTAL GEOLOGY

正20142512Chen Xiaoan(Jiangxi Provincial Research Institute of Soil and Water Conservation,Nanchang 330029,China);Yang Jie Distribution Characteristics and Causes of Collapse Erosion(Journal of Mountain Research,ISSN1008-2786,CN51-1516/P,31(6),2013,p.716-722,2illus.,7tables,14refs.)     

SEISMIC GEOLOGY

正20140644Cao Ying(Earthquake Administration of Yunnan Province,Kunming 650224,China);Wu Xiaoping Research on Structural Stress Field Basing on Focal Mechanism Solutions Data in Sichuan-Yunan Area(Journal of Seismological Research,ISSN1000-0666,CN53-1062/P,36(2),2013,p.165-172,6illus.,2tables,16refs.)     

METALS DEPOSITS

正20140806Cai Jinhui(Wuhan Center of China Geological Survey,Wuhan 420205,China);Wei Changshan Zircon U-Pb Ages of Magmatic Rocks of Dabaoshan Molybdenum-Polymetallic Deposit,Guangdong Province(Geolo-     

EXPLORATION ENGINEERING

正20141251Ban Junsheng(Central Laboratory,Second Geological Team,Henan Provincial Non-Ferrous Metals Geological and Mineral Resources Bureau,Pingdingshan 467021,China);Ren Jinxin Determination of the Magnetic Material Composition in Magnetite Ore