Mo稳定同位素研究进展

随着表面热离子质谱(TIMS)和多接收器电感耦合等离子体质谱(MC-ICP-MS)的广泛应用以及同位素分析方法的改进,近10年来非传统稳定同位素(Cu、Zn、Fe、Se、Mo、Cr、Hg等)的研究得到迅速发展.其中,由于Mo同位素的分馏明显受氧化还原条件的控制,使其在指示古环境及古气候的变化方面有独特的地球化学指示意义.同时,Mo同位素在指示成矿物质来源和海洋Mo循环等方面也取得较大成果.因此,Mo同位素地球化学研究已成为国际地学领域的一个前沿和热点.本文综合前人的研究成果,结合近期自己的工作,论述了Mo同位素地球化学研究领域的一些重要进展,详细介绍了Mo同位素的化学分离、提纯和质谱分析技术,并对其应用前景进行了展望.     

多接收电感耦合等离子体质谱Cu同位素测定中的干扰评估

多接收电感耦合等离子体质谱（MC—ICP—MS）是高精度测定铜同位素的新方法,然而在测定中也可能存在干扰。为此对MC—ICPMS Cu同位素测定中的可能干扰进行了评估。主要包括以下方面的内容：（1）对所用标准物质和试剂进行了纯化,所用标准物质和试剂对Cu同位素的同质异位素干扰可以忽略;（2）运用K和／参数进行了讨论,其中K为样品中的Cu浓度与标准溶液中Cu浓度的比值,f为在一定Cu浓度的标准溶液中干扰信号相对于^63Cu真实信号的比值。理论模拟表明,当K值小于1时,即使在质量为63处的干扰很小,对ε^65 Cu的影响也可能很大;（3）通过对理论模拟结果与实际测定结果的对比,发现对所用的试剂而言质量数为65的干扰可以忽略不计;（4）实际测定结果表明,当样品中Cu的浓度是标样中Cu的浓度的0．5～4倍时,测试获得的样品的ε^65值与其真值在误差范围内一致;（5）对潜在的基质效应重点研究了Fe和Co对Cu同位素测定的影响。实验结果表明,当Fe／Cu〈100,Co／Cu〈7时,Fe,Co不影响Cu同位素比值的测定;（6）10个月的重现性研究结果为ε^65=3．5±1．0（2SD）。该测定值在误差范围内与文献报道的值一致     

Ablation Characteristic of Ilmenite using UV Nanosecond and Femtosecond Lasers: Implications for Non‐Matrix‐Matched Quantification

Ilmenite (FeTiO₃) is a common accessory mineral and has been used as a powerful petrogenetic indicator in many geological settings. Elemental fractionation and matrix effects in ilmenite (CRN63E‐K) and silicate glass (NIST SRM 610) were investigated using 193 nm ArF excimer nanosecond (ns) laser and 257 nm femtosecond (fs) laser ablation systems coupled to an inductively coupled plasma‐mass spectrometer. The concentration‐normalised ⁵⁷Fe and ⁴⁹Ti responses in ilmenite were higher than those in NIST SRM 610 by a factor of 1.8 using fs‐LA. Compared with the 193 nm excimer laser, smaller elemental fractionation was observed using the 257 nm fs laser. When using 193 nm excimer laser ablation, the selected range of the laser energy density had a significant effect on the elemental fractionation in ilmenite. Scanning electron microscopy images of ablation craters and the morphologies of the deposited aerosol materials showed more melting effects and an enlarged particle deposition area around the ablation site of the ns‐LA‐generated crater when compared with those using fs‐LA. The ejected material around the ns crater predominantly consisted of large droplets of resolidified molten material; however, the ejected material around the fs crater consisted of agglomerates of fine particles with ‘rough' shapes. These observations are a result of the different ablation mechanisms for ns‐ and fs‐LAs. Non‐matrix‐matched calibration was applied for the analysis of ilmenite samples using NIST SRM 610 as a reference material for both 193 nm excimer LA‐ICP‐MS and fs‐LA‐ICP‐MS. Similar analytical results for most elements in ilmenite samples were obtained using both 193 nm excimer LA‐ICP‐MS at a high laser energy density of 12.7 J cm^?2 and fs‐LA‐ICP‐MS.     

一次强对流的三维数值模拟分析

利用中国科学院大气物理研究所的完全弹性三维雹云数值模式（IAP—CSM3D）,对2007年7月21日发生在湛江的一次强对流进行数值模拟,分析了强对流的气流结构、垂直涡度、雷达回波及含水量分布变化特征。结果表明,模拟的回波最大强度与雷达实测结果较吻合。模拟的强对流发展阶段气流结构的典型特征为下层水平辐合,上层水平辐散,气流在5km高度发生转向;处于成熟阶段的底层辐合比发展阶段的更强。随着时间的推移,近地层气流先辐合后辐散,下沉辐散气流一直持续到冰雹云消散。模拟的风暴云高含水量中心与强回波中心相对应,出现在上升气流最大区域附近,这说明该风暴云的动力场与物质场配合较好。     

呼伦湖流域氢氧稳定同位素特征及其对水体蒸发的指示作用

以呼伦湖流域为例研究该区域氢氧稳定同位素在不同水体中的分布特征,并探讨氢氧稳定同位素对在该区域水文过程的指示作用.流域湖水、入湖河水、周边地下水水样的氢氧稳定同位素分析结果表明,夏季8月份湖水中的重氢氧稳定同位素比7月份的更加富集.而河水中氢氧稳定同位素在同一时间内的河流沿程上存在明显的差异,下游水体中的氢氧稳定同位素要比上游更加富集.研究区的河水和湖水的δ~(18)O-δD关系特征显示,河水和湖水的δ~(18)O-δD的关系点全部位于当地降水线的右下方,说明流域河水和湖水水体受到明显的蒸发作用.而井水的δ~(18)O-δD的关系点大都靠近当地大气降水线,说明这一区域的地下水主要是大气降水渗入地下形成.利用氢氧稳定同位素分馏过程中的氢氧稳定同位素的比率与剩余水体的关系,并在考虑湿度因子的动力分馏模拟下,计算出河水的剩余水体比例在0.85~0.96之间,而湖水的剩余水体比例在0.71~0.77之间.最后,利用氢氧稳定同位素质量平衡法对呼伦湖多年平均蒸发量进行了估算,估算的湖泊蒸发量结果与实测值相近,相对误差为5.4%,说明方法可靠.氢氧稳定同位素对于研究区域水文过程有着重要的作用,在今后呼伦湖流域水文研究中有着更加广泛的应用空间.     

菹草、伊乐藻对沉积物磷形态及其上覆水水质的影响

采集武昌南湖湖水、沉积物进行沉水植物的盆栽试验,试验设置沉积物未施磷处理和施100mg/kg磷处理,分别对应沉积物低内源磷和高内源磷状态,同时种植菹草、伊乐藻,以研究沉积物中磷形态及上覆水水质的变化特点.研究从2007年9月15日开始,历时160d.结果表明,高内源磷沉积物处理后,上覆水中水溶性总磷含量在沉水植物的作用下明显降低;种植沉水植物可使水体总磷、总氮、叶绿素a含量显著降低,且伊乐藻对总磷的净化效果优于菹草;沉水植物对高内源磷沉积物的上覆水中叶绿素a的控制比对低内源磷条件下的效果更好;无论沉积物是否输入磷,在盆栽条件下,上覆水中叶绿素a随时间的变化均能较好地用一级动力学模型来描述;上覆水TDP、TP与沉积物中Ca_(10)-P之间有极显著正相关;种植菹草或伊乐藻的沉积物中Ca_(10)-P与上覆水中TDP和TP的相关系数分别为0.990(P≤0.01)和0.977(P≤0.05).     

新疆阿尔泰可可托海伟晶岩型稀有金属矿床中磷灰石地球化学特征及意义

磷灰石可以记录和保存岩浆和热液活动的信息。可可托海伟晶岩型稀有金属矿床磷灰石发育,为研究该矿床伟晶岩成岩成矿过程提供了优良的条件。已有对可可托海伟晶岩型稀有金属矿床磷灰石的研究集中在其稀土元素特征,较少讨论其对伟晶岩成岩成矿过程的制约。本文选取可可托海伟晶岩型稀有金属矿床富矿伟晶岩脉（3号脉）和相对贫矿伟晶岩脉（1号、2b号和3a号脉）中的磷灰石作为研究对象,进行磷灰石岩相学和地球化学研究。岩相学分析表明,磷灰石主要与钠长石、石英、白云母、锰铝榴石等伴生。EPMA分析显示,磷灰石F含量为3.67%~4.41%,Cl含量小于0.67%,较低的Cl含量表明伟晶岩熔体出溶的流体Cl含量较低;大部分磷灰石MnO含量为4.67%~8.71%,但2b号脉磷灰石MnO含量变化较大（1.23%~14.28%）,这是由于2b号脉磷灰石具有分带结构,暗示其遭受后期热液作用,促使磷灰石溶解-再沉淀,导致MnO含量发生较大变化。LA-ICP-MS分析显示,贫矿伟晶岩脉磷灰石的稀土元素含量较低（< 180×10^-6）;相反,富矿伟晶岩脉磷灰石的稀土元素含量较高（>700×10^-6）,并具有明显的四分组效应（TE_1-3平均值为1.7）。1号脉和3a号脉磷灰石均显示轻稀土元素富集,反映其形成过程中有含Cl热液的参与。3号脉磷灰石显示强烈Eu负异常和Ce正异常,而2b号脉磷灰石显示强烈Ce负异常和中等Eu负异常,这种Eu、Ce异常的差异可能与岩浆-热液阶段大量流体出溶密切相关。磷灰石的沉淀将导致热液中HF含量的降低,促使磷灰石周围铌钽矿结晶和Nb、Ta进入磷灰石中。可见,在伟晶岩形成过程中,磷灰石并非保持稳定,其分带结构和主微量成分变化记录了后期热液活动,暗示后期热液活动对伟晶岩的成矿具有重要作用。

     

Water-rock-tailings interactions and sources of sulfur and metals in the subtropical mining region of Taxco,Guerrero (southern Mexico): A multi-isotopic approach

Multi-isotope (H, O, S, Sr, Pb) systems coupled with conventional (major and trace element) hydrogeochemical analysis were applied to determine the origin of water, to model water-rock-tailings interactions and for source apportionment of sulfur and associated toxic metals in the mining region of Taxco, Guerrero in southern Mexico. Oxygen and H isotopes indicate that meteoric water in the zone is rainwater undergoing varying degrees of isotopic fractionation by atmospheric evaporation whereas Sr isotopes trace the interaction of pristine water from volcanics of the regional recharge zone and subsequently flowing through sandstone and shale to spring points. Leachates form from two distinctive sources (spring water and surface water) having differential interactions with bedrocks prior to entering the tailings. Compared to pristine water, leachates are enriched in sulfate, metals (e.g. Fe, Mn, Pb and Zn) and metalloids (e.g. As). The sulfur isotopic composition of ore-sulfides, leachates, secondary precipitates, regional surface water and hypogenic sulfates is described in terms of a two-component mixing model with shale of Mexcala and limestone of Morelos formations representing the light and heavy end-members, respectively, whereas Sr isotopic composition is bracketed combining three lithogenic (Mexcala/Morelos, Tilzapotla and Taxco Schist) sources. Finally, leachates have a mixture of lead from ore-sulfides and Taxco Schist Formation (Family I) or from ore-sulfides alone (Family II). The application of multiple environmental isotopic techniques is an outstanding tool for elucidating complex interactions of water with bedrocks and tailings and for determining the source of sulfur and toxic metal from mining and other metal polluted environments.     

西天山巴音布鲁克地区早古生代成矿地质环境:岩浆岩及其时代和元素同位素约束

西天山位于中亚造山带(CAOB)西南部,是其重要组成部分。CAOB晚古生代金属成矿环境和过程尤为典型,但早古生代成矿地质环境还不甚清楚。新疆巴音布鲁克地区出露(原定时代晚志留世)巴音布鲁克组火山岩夹浅海相碎屑岩和灰岩,是认识西天山早古生代成矿地质环境的难得对象。巴音布鲁克组出露于Nikolaev-那拉提山北缘断裂与Atbash-Inylchek-那拉提山南缘断裂之间的中天山,在巴音布鲁克地区典型发育,火山岩包括玄武岩、玄武安山岩、英安岩、流纹岩及相应的火山碎屑岩,其中侵入岩有正长斑岩和花岗闪长岩。LA-ICP-MS测得玄武安山岩、英安岩、正长斑岩、花岗闪长岩、流纹岩锆石U-Pb年龄分别为455.6±8.1Ma、444.5±1.9Ma、441.4±1.6Ma、455.4±5.3Ma、424±1.9Ma,岩浆活动于晚奥陶-早志留世,喷出和侵入时代接近,原定巴音布鲁克组地层时代晚志留世应改为晚奥陶-早志留世。这些岩浆岩具有相似的稀土元素地球化学特征,微量元素相比原始地幔均亏损Nb、Ta、P、Ti。玄武岩正的ε(t)=+1.6~+6.7,低的(~(87)~Sr/~(86)NdSr)i=0.70377~0.70489,指示岩浆源区具有亏损地幔特征,弱的Zr-Hf负异常,低的Th/Nb比值,较窄的同位素变化范围暗示地壳混染并不显著,微量元素及铅同位素特征(~(206)Pb/~(204)Pb=18.26~18.77,~(207)Pb/~(204)Pb=15.63~15.69,~(208)Pb/~(204)Pb=38.21~38.34)表明岩浆源区可能是俯冲流体及洋底沉积物交代的地幔楔橄榄岩部分熔融成因。西天山巴音布鲁克地区早古生代岩浆岩应是南天山洋晚奥陶-早志留世向北向中天山陆块之下俯冲在中天山-伊犁板块南缘活动大陆边缘的岩浆产物,指示了陆缘岩浆弧环境。这种陆缘弧环境有利于斑岩铜金成矿系统发育,值得高度关注相关铜金矿的地质找矿。     

Geodynamic setting,structure, and composition of continuous trachybasalt-trachyandesite-rhyolite series in the north of Altai-Sayan area: the role of crust-mantle interaction in continental magma formation

The geologic positions and geochemical and isotope parameters of the Ordovician-early Silurian and Early-Middle Devonian continuous volcanic series of the Minusa basin and its mountainous framing are compared. Both series are composed mostly of moderately alkaline rocks with variations in SiO₂ contents from 45 to 77 wt.%. The Ordovician-early Silurian series differs from the Early-Middle Devonian one in lower contents of TiO₂ (< 1.7 wt.%) and Fe₂O_3tot and higher contents of Al₂O₃ in all rock varieties and in the more fractionated REE patterns of trachybasalts. The compositions of both series reflect two simultaneous mechanisms of magma evolution. The main process was fractional crystallization leading to the formation of rocks from trachybasalts to trachyrhyodacites. The accessory mechanism was the contamination of fractionated melts by crustal material, anatectic melting of crust, and mixing of deep-seated magmas with crustal melts. These processes had specifics at each stage and were controlled by the composition of the sources of parental melts. Their geochemical and isotopic parameters (high alkalinity, high contents of lithophile elements, negative anomalies of Nb, Ta, and Ti, and enrichment in radiogenic Sr) point to the interaction of mantle plumes with the lithospheric mantle that was metasomatically transformed during the preceding Vendian-early Cambrian subduction processes.