华南寒武纪早期牛蹄塘组黑色岩系中Ni-Mo多金属硫化物矿层的Mo同位素组成讨论

华南寒武纪早期牛蹄塘组黑色岩系底部赋存有一层富Ni-Mo多金属元素的硫化物矿层.Lehmann等(2007)报道Ni-Mo矿石的Mo同位素组成十分均一,δ98/95MoMOMO值为-1.24‰±0.10‰;而赋矿围岩黑色页岩的Mo同位素组成变化较大,δ98/95MoMOMO值为-1.82‰～-0.40‰,并认为Mo全部来源于海水.笔者发现,含Mo低的黑色页岩具有Mo含量与Mo同位素组成的正相关关系,可能反映了海水来源Mo(以富重Mo同位素为特征)与页岩中碎屑组分来源Mo(以富轻Mo同位素为特征)两者的混合.Ni-Mo矿石非常均一的Mo同位素组成可能反映了它们的Mo来源既不是海水,也不是碎屑组分,而很可能是第3种来源,即以海底热液占主导.有必要对含矿与不含矿的该套黑色岩系开展更详细的Mo同位素研究,以便进一步确定寒武纪早期海水的Mo同位素组成和Ni-Mo矿层的成因.     

华南下寒武统Ni-Mo-Se多金属层S-Se同位素体系

为了进一步理解华南下寒武统Ni-Mo-Se多金属层的物质来源及形成环境,文中分析了遵义中南村和张家界后坪两个Ni-Mo-Se矿层及其围岩的黄铁矿硫同位素和全岩的硒同位素组成。硫同位素组成显示两个Ni-Mo-Se矿层形成时的环境存在区域性差别,中南村矿层形成于间歇开放的海洋环境,而后坪矿层形成于封闭的缺氧（静海）环境。较大的硫同位素范围暗示硫酸盐还原菌控制硫同位素的分馏,而热液流体可能提供了大量金属元素,从而导致矿层富集大量的硫化物和稀有金属。硒同位素组成指示牛蹄塘组底部热液流体的Se可能重新经历了氧化还原循环,而Se的富集过程可能受有机质和粘土矿物吸附或类质同象过程控制。因此,控制多金属富集的因素主要为富集金属的热液流体的参与和缺氧环境下的自生沉积。     

华南下寒武统Ni-Mo-Se多金属层S-Se同位素体系

为了进一步理解华南下寒武统Ni-Mo-Se多金属层的物质来源及形成环境,文中分析了遵义中南村和张家界后坪两个Ni-Mo-Se矿层及其围岩的黄铁矿硫同位素和全岩的硒同位素组成。硫同位素组成显示两个Ni-Mo-Se矿层形成时的环境存在区域性差别,中南村矿层形成于间歇开放的海洋环境,而后坪矿层形成于封闭的缺氧(静海)环境。较大的硫同位素范围暗示硫酸盐还原菌控制硫同位素的分馏,而热液流体可能提供了大量金属元素,从而导致矿层富集大量的硫化物和稀有金属。硒同位素组成指示牛蹄塘组底部热液流体的Se可能重新经历了氧化还原循环,而Se的富集过程可能受有机质和粘土矿物吸附或类质同象过程控制。因此,控制多金属富集的因素主要为富集金属的热液流体的参与和缺氧环境下的自生沉积。     

雪峰山西侧地区下寒武统牛蹄塘组烃源岩特征与油气地质意义

通过对雪峰山西侧地区下寒武统牛蹄塘组烃源岩的系统观测、采样和有机地球化学研究,总结了烃源岩的分布规律、有机质母质类型、烃源岩形成与沉积环境的关系、有机质成熟度等。牛蹄塘组烃源岩具有高有机碳、低氯仿沥青“A”、低生烃潜能的特征,有利烃源岩主要分布在黔北遵义、黔东天柱—城步、渝东南—湘西酉阳—麻阳一带及鄂西咸丰—张家界一带。干酪根镜下鉴定表明,有机质以腐泥组为主(75%~93%),饱和烃/芳烃占0.84%~27%,平均5.77%,牛蹄塘组烃源岩有机质类型为Ⅰ型。干酪根δ13Corg较轻,为-34.99‰~-25.36‰,平均-31.80‰,显示沉积母质以浮游生物及海洋性自养菌为主,部分样品有机质来源以藻类为主,结合Pr/ph分析,烃源岩主要形成于缺氧且通常是超盐度的环境中。沥青反射率为2.23%~4.32%,平均3.45%,等效镜质体反射率为1.84%~3.23%,平均2.43%,表明大部分样品已达到过成熟阶段。     

贵州丹寨南皋下寒武统牛蹄塘组黑色页岩孔隙结构特征

页岩孔隙结构特征研究对页岩含气性评价具有重要意义。以上扬子东南缘南皋剖面下寒武统牛蹄塘组页岩储层为例,应用场发射环境扫描电子显微镜观察了页岩纳米级孔隙微观形态,通过低温氮气吸附法测定了页岩的氮气吸附等温线,并结合X-衍射矿物定量分析和有机碳含量测定,探讨了纳米级孔隙发育的控制因素。研究结果表明:矿物成分主要为黏土矿物(伊利石和少量绿泥石)、石英、长石、重晶石和石膏等。石英含量相对较高且沿剖面向上降低,wB平均为53%;相反,黏土矿物含量较低且沿剖面向上增加,wB平均为34%;碳酸盐矿物较少,仅在顶部可见。页岩主要发育粒内孔、粒间孔、裂缝和有机质孔4种孔隙类型,其中前两者较为常见。根据氮气吸附-脱附曲线、孔径分布特征、孔体积和比表面积可将样品划分为4类黑色页岩,孔隙以似片状颗粒组成的非刚性聚合物的槽状孔为主,前3类黑色页岩的孔径分布呈双峰形态,第4类黑色页岩的孔径分布呈单峰形态,最可几孔径分别为d≈0.9nm和d≈3.5nm。孔体积在0.002 8~0.024 3cm3/g之间,平均为0.014 7cm3/g,比表面积在1.056 8~28.825 0m2/g之间,平均为17.541 8m2/g,4类黑色页岩微孔频率分布依次减小,而介孔和宏孔频率分布逐渐增加,即微孔性逐渐变差,至第4类黑色页岩几乎只有宏孔孔隙。有机质丰度和矿物组分控制丹寨南皋牛蹄塘组黑色页岩的孔隙发育,其中有机质有利于孔隙发育且有机质微孔是孔体积和比表面积的主要贡献者;石英有利于孔隙发育,而黏土矿物则降低黑色页岩的孔隙性;它们均主要通过控制微孔和介孔的发育来控制黑色页岩的孔隙发育。     

贵州金沙下寒武统牛蹄塘组中的高肌虫

描述了贵州金沙岩孔镇长岩沟下寒武统(纽芬兰统一寒武系2统)牛蹄塘组底部黑色页岩中呈碳质薄膜保存的高肌虫化石,共2属1种1相似种和1未定种:朵氏昆明虫Kunmingella douvillei,昆明虫(未定种)Kunmingella sp.和新月形遵义虫相似种Tsunyiella of luna.这些高肌虫化石与最古老的三叶虫Tsunyidiscus(Mianxiiandiscus)共生,其层位可与云南的Abadiella带对比,表明Kunmingella和Tsunyiella的下限层位已下延至筇竹寺阶的底部.本应属于早寒武世高肌虫分布中区的金沙一带却发现了两区的典型分子Kunmingella和中区的Tsunyiella,说明两区与中区间的混生区的范嗣应从长宁-镇雄小区扩大至贵州的金沙和织金一带.贵州寒武系底部大量高肌虫的发现丰富了牛蹄塘生物群的组成,对研究寒武纪早期生物的演化具有一定的意义.     

湘西北下寒武统牛蹄塘组页岩气储集条件研究

为客观评价湘西北地区下寒武统牛蹄塘组页岩气资源勘探潜力,本研究利用X射线衍射仪（XRD）、高倍扫描电镜、扫描探针显微镜等系统研究了其页岩气储集条件。XRD分析结果表明, 泥页岩中脆性矿物含量为53.8%-98.1%, 平均77.9%,脆性矿物含量丰富,其高值区主要分布在张家界柑子坪、三岔及其周边地区。高倍扫描电镜分析结果显示,湘西北下寒武统牛蹄塘组泥页岩中发育残余原生孔隙、有机质微孔隙、不稳定矿物溶蚀孔、矿物层间微裂隙和构造裂缝,其中构造裂缝、有机质微孔隙和不稳定矿物溶蚀孔是页岩基质孔裂隙的主要组成部分。扫描探针显微镜分析结果显示,湘西北下寒武统牛蹄塘组泥页岩中蜂窝状的有机质丰富,主要呈分散状和条带状分布,其内部纳米级孔隙发育。Ultrapore-200A氦孔隙仪测试结果显示,湘西北下寒武统牛蹄塘组泥页岩孔隙度较低,为0.6%～11.7%,平均4.6%,其影响因素主要是构造裂缝,其次是泥页岩有机碳含量和长石含量。ULTRA-PERMTM200渗透率仪测试结果显示,湘西北下寒武统牛蹄塘组泥页岩的渗透率度较低,为 0.002mD~0.06mD,平均0.014mD,其影响因素主要是构造裂缝,其次是矿物层间微裂隙。等温吸附实验结果表明,湘西北下寒武统牛蹄塘组泥页岩具有较好的吸附气性能,其影响因素主要是有机碳含量,其次是粘土矿物含量。     

湘西下寒武统牛蹄塘组地球化学特征及其对沉积-构造环境的响应

为深入探讨湘西地区下寒武统牛蹄塘组黑色岩系沉积-构造环境,对三岔剖面黑色岩系进行了详细采样测试,并重点分析了主量、微量及稀土元素地球化学特征。研究结果表明,牛蹄塘组黑色岩系不仅有机碳含量高,而且相比于北美页岩更富集V、Ni、Cr等微量元素。δ~(13)C_(org)及微量元素判别指标V/(V+Ni)、V/Cr、Ni/Co、δU、Ce/La、Ce_(anom)等特征的变化均反映牛蹄塘组沉积期水体属缺氧还原的浅水环境,且Mo/TOC与U_(EF)-Mo_(EF)协同模式表明沉积区当时为一局限海盆环境。稀土元素(REE)中轻稀土相对重稀土富集,且北美页岩标准化分布模式呈近水平略微左倾状,结合元素比值特征和La/YbCe/Yb、La/Yb-ΣREE图解,牛蹄塘组黑色岩系的母岩以长英质岩石为主,但沉积过程也受到海底热液作用影响。同时,根据δCe、δEu的特征与K_2O/Na_2O-SiO_2图解,认为沉积区在早寒武世为被动大陆边缘构造背景。     

雪峰古隆起边缘下寒武统牛蹄塘组页岩气成藏地质特征及有利区预测

雪峰古隆起边缘下寒武统牛蹄塘组页岩具有良好的生烃和储集条件,是重要的页岩气勘探层位,但受多期构造运动改造,页岩气保存条件复杂,页岩气勘探一直未获突破.基于野外地质调查、钻探资料,结合有机地化分析测试等手段,对雪峰古隆起边缘即沅麻盆地及周缘下寒武统牛蹄塘组页岩气地质条件和勘探前景进行综合评价.研究表明:牛蹄塘组沉积于深水陆棚相,页岩有机碳含量TOC值普遍大于2.0%,一般在3.0%~5.0%之间;有机质类型为Ⅰ型;有机质成熟度2.17%~3.38%之间,平均为2.79%;页岩碎屑矿物平均含量77.25%;粘土矿物平均含量22.71%,硅质含量高,脆性较大,易于储层改造.综合地化、储层物性及保存条件等评价指标,提出沅麻盆地草堂凹陷及古隆起北缘凤凰-吉首-张家界一带为牛蹄塘组页岩气勘探有利区带.      

Occurrence modes of silver in the Ni-Mo-PGE polymetallic layer of the Lower Cambrian black shales in Zunyi,Guizhou Province,South China

The Ni-Mo-PGE polymetallic mineralization of the Lower Cambrian black shales locate in Zunyi, South China and contain abundant noble metals such as Ag, Au and PGE, and especially Ag with average concentration of 64×10-6. The occurrence modes of Ag have been investigated using methods of selective chemical dissolution and transmission electron microscopy. The results demonstrate that the occurrence modes of Ag are complex and diversiform. It might be associated with clay minerals, organic matter, sulfides and also occurred as native silver and sulfides with nanometer in size. Combined with results of previous studies, we suggest that the sulfides, clay minerals and organic matter which hosted in the Ni-Mo-PGE polymetallic ores of black shales can play the roles of important reduction and adsorption geochemical barriers for the enrichment and distribution of silver. This study further implies that the selective chemical dissolution and transmission electron microscopy may pave the way to study the occurrence modes of other noble metals in black shales.     

Large Zn isotope variations in the NiMo polymetallic sulfide layer in the lower Cambrian,South China

In South China, black organic-rich shales in the lower Cambrian Niutitang Formation host a NiMo polymetallic sulfide layer that discontinuously extends over ~1600 km. Seawater and hydrothermal origins are among the many suggested hypotheses and are still under debate. In order to discriminate Zn sources, we report Zn isotopes in NiMo polymetallic sulfide layers and their host shales from the Nayong and Zunyi locations in Guizhou province and the Zhangjiajie section in Hunan province. In each section, host organic-rich shales show homogeneous Zn isotope compositions which likely resulted from quantitative scavenging of dissolved Zn from seawater under euxinic conditions. The difference in the average δ⁶⁶Zn values of organic-rich shales between the two sections in Guizhou (0.76 ± 0.09‰) and one section in Hunan (0.59 ± 0.10‰) might reflect variations of Zn isotope gradient with the depth of seawater. Therefore, the organic-rich sediments need not always represent an isotopically light Zn sink, which is dependent on Zn isotope fractionation in the local basin. However, the δ⁶⁶Zn values in the NiMo polymetallic sulfide layers are different from those of their host shales, indicating that these sulfide layers did not inherit the Zn isotope signal of seawater. Based on the regular increasing trend in δ⁶⁶Zn values from Nayong (0.54 ± 0.06‰) to Zhangjiajie (1.34 ± 0.09‰) and the presence of PbZn mineralization in the Dengying/Doushantuo Formations, we argue that hydrothermal fluids associated with PbZn mineralization could be a major source of Zn in NiMo sulfide layers, especially in the Nayong location. A possible model is that the hydrothermal fluids related to MVT-type mineralization got overprinted on a multiple-sourced synsedimentary sulfide-rich layer. We provide additional evidence that Zn isotopes have great potential as a tracer of metal source and can be applied to similar types of mineralization as e.g., the late Devonian Ni-Zn-PGE Nick deposit (Selwyn Basin, Canada) or elsewhere.     

遵义松林镍钼多金属层铀存在形式及成因探讨

贵州省遵义松林地区下寒武统牛蹄塘组镍钼多金属层富集U、Mo、Ni、Re、Tl等元素.本文以松林地区镍钼多金属层磷块岩为主要研究对象,在松林系统取样的基础上,开展化学分析、径迹蚀刻、扫描电镜、能谱面扫描、浸出实验等工作.结果表明下寒武统牛蹄塘组镍钼多金属层中Ni、Mo显著富集,达到工业品位,U、Re、Tl明显富集.径迹蚀刻实验揭示铀主要富集于磷块岩碎屑边缘有机碳外带,为进一步确定铀的赋存形式圈定重点观察区.该区镍钼多金属层中铀呈晶质铀矿形式赋存于溶蚀重结晶磷块岩的溶蚀孔洞、微裂隙或微孔隙中,并与中高温热液矿物针镍矿、辉砷镍矿、闪锌矿、方铅矿、磷灰石共生.浸出实验采用去离子水、H2 SO4、NaHCO3+MnO2三种介质浸出样品中水溶态、酸可溶态、氧化可溶态的铀.80℃,48 h条件下浸出实验结果显示多金属磷块岩由黑色褪色为浅灰色、灰色,碳质页岩实验前后颜色均为黑色.遵义地区镍钼多金属层及碳质页岩中铀主要以吸附状态或独立矿物形式存在,以类质同象形式存在的难溶铀占比较小.研究认为,该区镍钼多金属层磷块岩中铀以独立矿物形式存在并与中高温热液矿物共生,为揭示扬子陆块东缘陆源裂陷环境下发生海底喷流和热水沉积作用提供新的微观证据.     

Selenium speciation in Lower Cambrian Se-enriched strata in South China and its geological implications

To understand the impact of Selenium (Se) into the biogeochemical cycle and implications for palaeo-redox environment, a sequential extraction method was utilized for samples including black shales, cherts, a Ni-Mo-Se sulfide layer, K-bentonite and phosphorite from Lower Cambrian Se-enriched strata in southern China. Seven species (water-soluble, phosphate exchangeable, base-soluble, acetic acid-soluble, sulfide/selenide associated, residual Se) and different oxidation states (selenate Se(VI), selenite Se(IV), organic Se, Se (0) and mineral Se(-II)) were determinated in this study. We found that the Ni-Mo-Se sulfide layer contained a significantly greater amount of Se(-II) associated with sulfides/selenides than those in host black shales and cherts. Furthermore, a positive correlation between the degree of sulfidation of iron (DOS) and the percentage of the sulfide/selenide-associated Se(-II) was observed for samples, which suggests the proportion of sulfide/selenide-associated Se(-II) could serve as a proxy for palaeo-redox conditions. In addition, the higher percentage of Se(IV) in K-bentonite and phosphorite was found and possibly attributed to the adsorption of Se by clay minerals, iron hydroxide surfaces and organic particles. Based on the negative correlations between the percentage of Se(IV) and that of Se(-II) in samples, we propose that the K-bentonite has been altered under the acid oxic conditions, and the most of black shale (and cherts) and the Ni-Mo-Se sulfide layer formed under the anoxic and euxinic environments, respectively. Concerning Se accumulation in the Ni-Mo-Se sulfide layer, the major mechanism can be described by (1) biotic and abiotic adsorption and further dissimilatory reduction from oxidized Se(VI) and Se(IV) to Se(-II), through elemental Se, (2) contribution of hydrothermal fluid with mineral Se(-II).     

Pediculate Brachiopod Diandongia pista from the Lower Cambrian of South China

The Chengjiang Lagerstatte has been celebrated for prolific soft-bodied fossils. Based on specimens recently excavated in the Chengjiang Lagerstatte by the Early Life Institute, Northwest University, Diandongia pista Rong, 1974, is directly revealed to be a pediculate brachiopod, assigned to the Family Botsfordiidae, as is further confirmed by the exceptionally preserved vascular system including dorsal and ventral mantle canals. These specimens described herein exhibit some peculiarities, notably the extremely thin and long pedicles, which suggest that Diandongia is epifaunal rather than burrowing brachiopod. A study of this group of animals indicates that they may be vital to understand the relationship between the lingulids and the remaining brachiopods, and the character evolution of the early Cambrian brachiopods.     

川北青川地区下寒武统沥青质砾石的发现及其意义

沥青质砾石被发现于四川省青川县白家镇一带的下寒武统碎屑岩中。黑色的沥青质砾石多呈次圆状或次棱角状,表面光滑但无光泽,与胶结物之间有明显的界线,直径最大可达5cm。推测这些砾石可能来自于被剥蚀的震旦系灯影组。沥青、碳酸盐岩和页岩以砾石的方式沉积于下寒武统．表明在早寒武世筇竹寺期之前川北青川地区已存在有古油藏,前寒武系中可能还有生烃的烃源岩。     

Silicalites of Hydrothermal Origin in the Lower Cambrian Black Rock Series of South China

A silicalite bed was found in the hanging wall and foot wall of the sulfide-rich bed of the Lower Cambrian black rock series in South China.Its origin was not described before,On the oxide(SiO2-Al2O3,SiO2-MgO,SiO2-k2o Na2O)diagrams for discriminating silicalites of chemical,biological and volcanic origins(Liu Xiufeng,1991),most of the data points of silicalites fall within the areas representing silicalites of chemical and volcanic origins.On the Al-Fe-Mn diagram for discriminating silicalites of hydrothermal and biological origins(Yamamoto,1987),the data points fall within the areas representing silicalites of hydrotermal and hydrothermal-biological origins.On the SiO2-Al2O3 diagram for discriminating silicalites of hydrothermal and hydrogenous origins(Bonatti,1975),the data points mostly fall within the hydrothermal area.The ratios of SiO2/Al2O3,SiO2/(K2O Na2O),SiO2/MgO,and K2O/Na2O in the silicalites stand between those of volcanic sediments and of seafloor hydrothermal sediments.The total amount of rare-earth elements in the silicalites is low;the North american Shale-normalized REE patterns decline leftward with obvious negative Ce anomaly.The trace elements Mo,Zn,As,Sb,Se,U,and Ba are higher than those in non-hydrothermal sediments and U/Th≥1.The present authors think that the silicalites are derived from seafloor hot brines which had attracted elements from igneous rocks.     

华南造山带下寒武统和中奥陶统发现放射虫

在华南造山带江西萍乡下寒武统牛角河组泥质板岩和湖南永州中奥陶统烟溪组硅质岩中首次发现放射虫。放射虫的发现表明萍乡—永州一带寒武纪—中奥陶世存在相当规模的处于低纬度的海盆。     

Pb-Pb dating of black shales from the Lower Cambrian and Neoproterozoic strata, South China

Black shales occur widely in the Lower Cambrian and Neoproterozoic strata on the Yangtze Platform, South China. In this study, Lower Cambrian black shales from Xiuning section and Late Neoproterozoic black shales from Weng’an section were studied and Pb isotopic compositions were analyzed following a stepwise acid-leaching technique. The ²⁰⁶Pb/²⁰⁴Pb ratios in both sections show large variations, from 18.906 to 43.737 in the Weng’an section and from 24.811 to 38.110 in the Xiuning section. In contrast, the ranges for ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values in both sections are relatively smaller from 15.649 to 17.126 and 37.744-38.199 in the Weng’an section, and from 16.034 to 16.783 and 38.602-39.391 in the Xiuning section, respectively. These data yielded two Pb isotope isochron ages of 536±39 and 572±36 Ma, respectively. These ages well accord with other published data and we suggest that they represent the depositional ages for the Lower Cambrian Hetang Formation and the upper Neoproterozoic Doushantuo Formation in South China.