238U/235U分馏及其地质应用

铀是自然界中天然存在的最重的放射性元素。传统观点认为²³⁸U/²³⁵U是不分馏的,但近些年的研究发现自然界中铀同位素分馏δ^238/235U可达1.3‰,远大于多接收电感耦合等离子体质谱仪（MC-ICPMS）的测试精度±0.2‰（2σ）。铀同位素的分馏机制与核场效应有关,自然界中最大的δ^238/235U分馏发生在氧化性沉积物（形成于氧化环境下的大洋锰结核富集轻铀同位素）和还原性沉积物（形成于还原环境下的黑色页岩富集重铀同位素）中,次氧化性沉积物和海水中δ^238/235U的分馏则小于前两者。由于具有对氧化-还原环境较敏感的特性,铀同位素被认为是理想的反演古海洋及古大气氧化还原环境变化的手段之一。δ^238/235U在形成于不同氧化-还原环境的高温型铀矿床（比如岩浆型）和低温型铀矿床（比如砂岩型）之间存在明显的同位素分馏,此特征可以作为确定铀矿床类型的重要依据。铀同位素分馏现象的发现,提示人们在应用Pb-Pb体系进行年轻地质体高精度测年时需要考虑到铀同位素分馏对测年精确度的影响。文章对近年来有关²³⁸U/²³⁵U的研究成果做了详细介绍,以推动铀同位素体系在地球科学领域的研究和应用。     

Origin of Paleoproterozoic Komatiites at Jeesiorova, Kittila Greenstone Complex, Finnish Lapland

Komatiites from the 2 Ga Jeesiörova area in Finnish Laplandhave subchondritic Al₂O₃/TiO₂ ratios like those in Al-depletedkomatiites from Barberton, South Africa. They are distinct inthat their Al abundances are higher than those of the Al-depletedrocks and similar to levels in Al-undepleted komatiites. Moderatelyincompatible elements such as Ti, Zr, Eu, and Gd are enriched.Neither majorite fractionation nor hydrous melting in a supra-subductionzone setting could have produced these komatiites. Their highconcentrations of moderately incompatible elements may haveresulted from contamination of their parental melt through interactionwith metasomatic assemblages in the lithospheric mantle or enrichmentof their mantle source in basaltic melt components. Re–Osisotope data for chromite from the Jeesiörova rocks yieldan average initial ¹⁸⁷Os/¹⁸⁸Os of 0·1131 ± 0·0006(2), _Os(I) = 0·1 ± 0·5. These data, coupledwith an initial _Nd of +4, indicate that melt parental to thekomatiites interacted minimally with ancient lithospheric mantle.If their mantle source was enriched in a basaltic component,the combined Os–Nd isotopic data limit the enrichmentprocess to within 200 Myr prior to the formation of the komatiites.Their Os–Nd isotopic composition is consistent with derivationfrom the contemporaneous convecting upper mantle. KEY WORDS: Finnish Lapland; Jeesiörova; komatiites; mantle geochemistry; petrogenesis; redox state; Re/Os isotopes; Ti enrichment     

The Occurrence of Forsterite and Highly Oxidizing Conditions in Basaltic Lavas from Stromboli Volcano, Italy

We report the occurrence of unusual, high-magnesium (Fo₉₆) olivinephenocrysts in a basaltic lava and an ejected lithic block fromthe Upper Vancori period (13 ka) and the recent activity (2002–2003)of Stromboli volcano, Italy. The samples that contain this distinctivemineral chemistry are a shoshonitic basalt and a basaltic andesitewith anomalous bulk-rock chemical characteristics in which theiron is highly oxidized (6–8 wt % Fe₂O₃ and <1 wt %FeO). In other respects these samples are similar to the majorityof Stromboli basalts, characterized by the coexistence of olivine,clinopyroxene, plagioclase and Fe–Ti oxides as phenocrysts,and clinopyroxene, plagioclase and Fe–Ti oxides in thegroundmass. In the high-magnesium olivine samples, Fe–Tioxides (pseudobrookite) typically occur as symplectitic intergrowthswith the olivine phenocrysts, indicating simultaneous growthof the two phases. We propose, as a paragenetic model, thatthe Fo₉₆ olivine phenocrysts crystallized from a highly oxidizedbasaltic magma in which most of the iron was in the ferric state;hence, only magnesium was available to form olivine. The highlyoxidized state of the magma reflects sudden degassing of volatilephases associated with instantaneous, irreversible, transientdegassing of the magma chamber; this is postulated to occurduring periods of sudden decompression induced by fracturingof the volcanic edifice associated with paroxysmic activityand edifice collapse. KEY WORDS: Stromboli; Mg-rich olivine; oxygen fugacity; redox state of magmas; irreversible processes     

修水地区下寒武统富铀地层特征及其铀富集机制研究

文章以修水地区下寒武统王音铺组至观音堂组下部富铀黑色页岩地层钻孔样品（U含量为9.37×10-6~202×10-6） 为研 究对象,进行了细致的显微观察和分析,并对该区下寒武统地层中U含量与沉积环境因素（沉积盆地中的生物生产力、底 层水体的氧化还原状态、及盆地与广海间的流通性） 之间的关系进行了探讨。结果表明,这些钻孔样品显示明显的沉积成 岩特征,未发现明显热液叠加/淋积作用现象,说明本区下寒武统地层只经历了沉积成岩作用,而没有经历过明显的热液作 用或者淋积作用。研究地层大部分样品中的U含量与TOC含量呈正相关,王音铺组上部U含量最高（202×10-6） 的样品沉积 时的初级生物生产力也最高。经扫描电镜观察和电子探针分析,发现其中有机质中包裹着沥青铀矿,两者关系密切,推测 U与有机质很可能是一起沉积-成岩富集的;在缺氧硫化的强还原沉积环境下沉积的王音铺组地层的U含量,明显高于在 缺氧非硫化环境下沉积的观音堂组下部地层中的U含量,而且在强还原硫化环境下,沉积时盆地处于开放流通性程度较高 时期的样品,其U含量明显高于盆地处于开放程度较低时期的样品。综合这些观察和分析得出,早寒武世王音铺组上部地 层沉积时,高生物生产力所形成的有机质降解时大量耗氧,导致底层水沉积环境处于强还原硫化状态,同时,沉积盆地处 于适当的开放程度,与广海之间水流交换使盆地上层含U氧化水体得到补充,U最终在底层水体强还原硫化环境下沉淀于 沉积物中,可达到较高程度的富集乃至矿化的水平。     

鄂尔多斯盆地纸坊组微量元素地球化学特征及沉积环境指示意义

沉积岩中的微量元素对沉积环境的水介质变化有着较高的敏感度,是研究沉积物沉积时的古气候、古环境的有效手段。鄂尔多斯盆地纸坊组是三叠系具有油气显示的新层系,其古气候及古水体环境对于恢复该时期盆地沉积格局、重建古地理及成藏研究具有重要意义。采用ICP-MS对鄂尔多斯盆地纸坊组剖面及岩芯21件泥岩及粉砂岩样品进行了微量元素测试,选择对沉积环境介质较为敏感的锶（Sr）、钡（Ba）、钍（Th）、铀（U）、钒（V）、镍（Ni）、钴（Co）等元素作为判别指标,并结合沉积学标志及孢粉分析,对鄂尔多斯盆地纸坊组沉积环境及古气候特征进行研究。结果表明:通过Li、Sr、Ni、Ga含量及Sr/Ba值判别研究区为淡水-微咸水沉积环境;U/Th值分布在0.09~0.38,δU值分布在0.43~1.07,V/（V+Ni）值分布在0.69~0.89,V/Cr值分布在0.87~5.57、Ni/Co值分布在1.21~2.93,指示水体分层不强的氧化-弱还原过渡环境;纸坊组水体深度平均深度小于30 m,大型"汇水"湖泊尚未形成;Sr/Cu比值在0.85~16.7之间,大部分小于10,仅个别值大于10,表明纸坊组古气候已由和尚沟组干热气候趋于温暖气候。     

An Improved Procedure for the Determination of Ferrous Iron Mass Fraction in Silicate Rocks Using a Schlenk Line‐Based Digestion Apparatus to Exclude Oxygen

Precise and accurate determination of ferrous iron mass fraction in silicate rocks and geological reference materials is still a significant challenge due to the labile nature of the analyte. Here, we report a modified and improved procedure for the determination of ferrous iron mass fraction, capable of yielding moderately accurate and highly precise results in a relatively shorter time than before. This modified technique requires a more convenient operational procedure than the classical method. A sample digestion apparatus was designed that included a Schlenk line to expel air in order to prevent oxidation. The advantages of this procedure over the classical procedure are shorter process flow, higher efficiency and absence of an additional redox indicator. The composition of the acid matrix used to dissolve the samples as well as the incubation temperature and time was investigated. Comparative data for twenty‐one reference materials are reported, with five of them reported for the first time by the Schlenk line procedure. A series of experiments were carried out to identify and minimise the main source of error. In addition, the possibility of eliminating the reducing substances before digestion, by pretreatment of the sample by cold 10% methanolic bromine, was also studied.     

安徽巢湖地区二叠系瓜德鲁普统孤峰组古环境演化

二叠纪瓜德鲁普世是古海洋条件发生重大变化的转折期。瓜德鲁普世古海洋、古环境的演化对古生代底栖无脊椎动物灭绝的影响仍然是个谜。利用元素地球化学,分析瓜德鲁普统孤峰组的陆源碎屑供应、海洋表层水体的初级生产力以及底部水体的氧化还原条件。结果表明:瓜德鲁普世早期和晚期分别发生了一次陆源碎屑输入的高峰期。瓜德鲁普世早期海洋初级生产力最高,中期海水初级生产力较低,而晚期稍有升高。瓜德鲁普世古海水主要为缺氧至硫化环境。瓜德鲁普世早期以贫氧至缺氧环境为主,间歇性出现硫化环境;中晚期则以硫化环境为主,间歇性出现缺氧环境。这些氧化还原环境的演化主要受到水动力条件的影响。瓜德鲁普世深水环境水体的持续缺氧硫化引发浅水台地底部水体的持续贫氧甚至缺氧,造成海洋生态系统变得脆弱,引发生物危机事件。     

基于微量元素分析的古沉积背景重建——以准噶尔盆地西北缘安集海河组为例

作为沉积背景变化的敏感性指标,微量元素丰度及其比值对物源构造背景识别、沉积环境恢复和古气候重建等具有重要意义。本文对准噶尔盆地西北缘古近系安集海河组23件泥质岩类样品开展微量、稀土元素分析测试,结合岩心与薄片等相标志,完成了研究区古沉积背景的恢复。研究表明：①稀土元素球粒陨石标准化分配模式、微量元素上地幔标准化蛛网图以及Th/Sc- Zr/Sc、La/Yb- REE、La- Th- Sc判别图解综合分析指示,安集海河组沉积期物源供给较为稳定,物源区风化程度较高,再旋回及分选作用不明显;沉积物源主要来自上地壳的长英质岩石,母岩岩石类型以酸性火成岩为主,主要为大陆岛弧成因,扎伊尔山早石炭世侵入岩是可能的物源区;②元素Li、Sr、Sr/Ba和Th/U组合以及U/Th、 δ U、 δ Ce、Ceanom和Ce/La组合指示,安集海河组沉积期表现为陆相半咸水的氧化型沉积环境,该沉积环境受古近纪系列热气候事件的影响,在极热气候背景下,湖盆水体蒸发强烈,湖平面略有下降且湖水浓缩,水体盐度增高,部分湖底沉积物因暴露水面而被氧化,该现象可在陆相红层的特殊沉积物中得到进一步印证;③纵向上,安集海河组Sr/Cu以及Cu和Cs含量变化整体呈上升趋势,反应气候的干旱程度不断增加,同时风化作用指数Rb/Cs整体呈下降趋势,表明受气候干旱的影响,该时期风化作用逐渐减弱。综上,安集海河组沉积期,研究区气候经历了由湿热向干热转变的过程。     

东海和冲绳沉积物中自生铀蓄积过程及控制机理

采用同位素稀释ICP-MS测定法,对中国东海陆架及日本冲绳海槽的6个沉积物芯中U和Th的同位素地球化学行为进行了研究,以了解氧化还原敏感元素U在近海次氧化性沉积物中的蓄积行为,并评价其在全球海洋铀平衡中的意义。东海沉积物芯中,238U浓度及238U/232Th比值随深度变化不明显。但是在冲绳海槽沉积物芯中,238U浓度及238U/232Th比值在沉积芯表层氧化带显示较低值,然后在次氧化层随深度增加而增加。230Th和232Th浓度在所有沉积物芯中基本不随深度变化。这些结果说明,冲绳沉积物中有“自生铀”的蓄积过程发生,蓄积速率约为(47±5)～(90±8)ng/(cm2·a),与文献报道的世界其他海域次氧化性沉积区大致相当。进一步证明了U在近海次氧化性沉积区的蓄积对于全球海洋铀平衡有重要意义。“自生铀”的主要蓄积机制是海水U(Ⅵ)向沉积物迁移,在还原条件下被还原为惰性的U(Ⅳ)并被吸附在沉积物固体相上。