重砂分级-扫描电镜-能谱等技术研究湖南张家界黑色页岩贵金属元素赋存状态

黑色岩系是多种有用元素的重要载体,Cu、Pb、Zn、Ni、Mo、V、U、Au、Ag、稀有和稀土元素在黑色岩系中异常富集,某些黑色岩系的贵金属(铂族元素、Au、Ag)也异常富集,其含量甚至部分超过了基性和超基性岩,这类黑色页岩矿床中铂族元素(PGEs)的赋存状态至今尚未有一个确切的定论。本文采集了湖南张家界属寒武系牛蹄塘组黑色页岩中Mo-Ni矿层作为研究样品,通过化学分析表明矿石中含Pt 531×10~(-9),Pd 514×10~(-9),Os 185×10~(-9),PGEs合量为1259.43×10~(-9),Au 332×10~(-9),Ag 12.2×10~(-6),已富集成矿。进一步利用重砂分级、化学分析、X射线衍射、扫描电镜及能谱技术研究了贵金属元素赋存状态,结果表明:①Ag:主要以独立矿物形式存在,少量以类质同象形式赋存在其他矿物中。独立矿物有砷铜银矿、硫锑铜银矿、硫锑铅银矿、锑银矿、硫银锡矿、硫砷银铅矿、银黄锡矿、辉银矿、锑-银-锡互化物;类质同象主要是银黝铜矿-银砷黝铜矿、含银方铅矿和含银砷铜矿等。②Au:未发现独立矿物,黄铁矿是重要载金矿物。③PGEs:未见独立矿物,在不同重砂分级样品中没有富集,具分散性,推测铂族矿物很可能是以纳米形式存在,建议今后研究选矿工艺时,可考虑从制取纳米材料的思路进行应用研究。本文Ag-Sn-Sb互化物的发现为研究黑色岩系多元素富集成因机制提供了重要物证。     

渝东漆辽剖面五峰组-龙马溪组页岩及残余干酪根中微量元素地球化学特征

为探讨渝东漆辽剖面五峰组-龙马溪组页岩及残余干酪根内部微量金属元素的赋存规律及其对页岩气生成的影响,对页岩及残余干酪根中的微量元素进行了分析测试。结果表明,多数微量金属元素在五峰组-龙马溪组页岩干酪根中较页岩中更为富集,稀土元素表现出轻稀土富集,重稀土亏损,明显Eu负异常,轻微Ce负异常的特征;说明漆辽剖面五峰组-龙马溪组页岩沉积水体为贫氧-缺氧的热水沉积环境,而热水沉积环境正是导致页岩中V、Ni、U高度富集的原因。     

湘西北下寒武统碳质页岩岩石学、岩石化学和地球化学研究

湘西北地区下寒武统含矿岩系有二种岩性组合,1.含磷岩系(夹镍钼金属层)、碳质页岩、黑色页岩组合,富集的元素有Ni、Mo、V、U、Se和p等;2.薄层硅质岩(夹薄层碳质页岩或含磷结核碳质页岩)、碳质页岩、黑色页岩组合,富集的元素有V、Cd、U、Cu、Mo和Ba等。岩石化学和微量元素分析表明,碳质页岩有机碳含量一般为3—13％,黄铁矿为2—5％,Ni和Mo为40—200ppm,V_2O_5为200—4000ppm,有些层位高达1—2％,U为50—100 ppm,其它Cu、Zn、Ba和p等元素也有不同程度的富集。金属层富集Ni、Mo、Se、U等元素,其含量比克拉克值高数百倍至数千倍。含矿岩系可分为三个类型:(1)镍钼多元素;(2)钒镉铀;(3)碳质页岩(石煤)。     

贵州开阳白马洞铀矿化岩层地球化学特征

贵州开阳白马洞铀矿是重要的蚀变型铀矿,通过对白马洞清虚洞组黑色蚀变岩及白云岩风化红粘土和寒武系牛蹄塘组黑色页岩的常量元素、微量元素和稀土元素组成的分析研究,发现铀元素含量与Re、Se、Pb、Cu、As、Sb、Tl、Zn、Ni、Mo、Co、S含量为正相关关系,铀含量高,则Re、Se、Pb、Cu、As、Sb、Tl、Zn、Ni、Mo、Co、S含量也高,其中As、Co、Mo、Ni、Re、Tl、Zn、S具有显著的正相关性,而且地表土壤中Se、V、Mo 等元素的富集是铀矿找矿的主要标志之一。根据白马洞清虚洞组、寒武系牛蹄塘组黑色页岩、灯影组硅化白云岩的稀土元素配分模式分析,硒富集和铀矿化矿源层不仅是牛蹄塘组黑色页岩,可能有更深部的矿源存在。认为硒富集区是铀矿找矿远景区域;古代炼汞矿渣富集铀矿,值得开发利用和治理。     

贵州铜仁地区九门冲组黑色页岩地球化学特征及成岩环境研究

贵州铜仁地区九门冲组黑色页岩富含钒、镍和铀等金属元素,也是一套优质烃源岩。为了解黑色页岩的沉积环境和成因,对其进行地球化学特征研究。结果表明：Zn、Cu、Cr、Ni、U元素富集,稀土总量较高,轻稀土富集。Ce负异常、V/Cr和V/（V+Ni）表明黑色页岩形成于静水还原的斜坡环境,Co/Zn值、Zn-Ni-Co三元图、（La/Sm）N＞1、δEu正异常、La/Yb-REE图解、La-Ce关系图解和北美页岩组合样标准化曲线略左倾等反映黑色页岩沉积过程受到热液活动的影响,海底热液提供了丰富的物质来源。根据K2O/Na2O-SiO2判别图、稀土元素组合及比值等特征,反映区内构造背景以被动大陆边缘为主,由于受到热液活动的影响,也显示活动大陆边缘构造背景的特征。     

四川盆地志留系龙马溪组富气页岩地球化学特征及沉积环境

为探讨四川盆地志留系页岩氧化还原条件和古沉积环境,并给页岩气下步勘探和有利区优选提供参考,选取W201和Z106两口龙马溪组页岩取心井,进行了主微量元素和有机地球化学分析。结果表明,W201井富有机质页岩Th/U、V/Cr和Ni/Co值分别为0.3~2.3,1.49~4.27和2.51~6.7,Z106井分别为0.45~2.15,1.34~5.61和3.64~11.96,稀土元素(δCe和δEu)与微量元素一致,结合黄铁矿和笔石富集程度,指示川南上奥陶统观音桥段沉积于氧化环境,龙马溪组底部富有机质页岩沉积于滞留缺氧的还原环境。早志留世的缺氧环境与全球海平面快速上升一致,对川南龙马溪组黑色页岩的形成具有明显控制作用,形成一套稳定发育的厚度为30~40m的黑色页岩,TOC含量为1.96%~4.28%,是目前页岩气勘探开发主力层段。     

黔北地区下寒武统底部黑色页岩沉积环境条件与源区构造背景分析

为了深入探讨黔北地区下寒武统底部黑色页岩的沉积环境条件和源区构造背景,对黔北地区下寒武统牛蹄塘组黑色页岩进行系统采样,对其微量元素和稀土元素地球化学特征进行了系统分析。研究表明,微量元素中高的WV/(WNi+WV)和U/Th比值等反映该区黑色页岩形成于海域开阔的还原环境。区内黑色页岩样品中Mo、Sb、U、Cd、 V、Ba、Tl、Ni、W、 Cr、Cs、Cu、Zn、Bi等元素的高富集以及正Eu异常和较低的Co/Zn比值均反映了黔北下寒武统底部黑色页岩受到深部热液活动的影响。根据主、微量和稀土元素组合及比值特征可以看出黔北地区下寒武统底部黑色页岩的源岩具有花岗岩、沉积岩和玄武岩等多成因性质。源区构造背景以被动大陆边缘为主,由于受深部热液活动的影响,也显示大陆岛弧构造背景的特征。     

中、下扬子地区下寒武统黑色页岩微量元素富集特征

中国南方扬子地区下寒武统黑色页岩分布广泛,主要由黑色页岩、黑色白云质页岩,黑色粉砂质页岩和黑色硅质页岩等组成;并伴生有较厚的磷块岩矿床、钒矿床和镍、钼多元素硫化物矿床。对黑色页岩岩石学特征、元素地球化学特征进行系统研究,并详细分析微量元素的富集成因,结果表明：黑色页岩主要形成于静水还原的浅海-半深海缓坡环境,层状元素富集带为沉积成因,海底热流体提供了丰富物质来源。总体上,Co、Be、Mn、Ga等元素含量较低;Cu、V、Ni、Mo等元素的含量较高,多数超过北美页岩平均值;以Ni、Mo为主的多元素富集层通常位于磷块岩之上,以黑色页岩、黑色白云质页岩中的硫化物和硫酸盐矿物为主要载体,其中有机碳（TOC）含量可达12.2%以上,远高于其他元素富集层,随着页岩内硅质成分增加,Ni、Mo、Fe、Co等元素含量明显降低;以V为主的多元素主要赋存于黑色硅质页岩中的水云母,与页岩内硅质成分具有较好的正相关关系;黑色页岩中稀土元素含量为(76.22~290.67)×10-6,轻重稀土比值LREE/HREE介于1.21~4.22,说明轻稀土更为富集,Sr/Ba值为0.04~0.34,δEu正异常,且北美页岩标准化配分曲线呈现平缓左倾,为沉积过程中存在海底热水流体提供了进一步证据。     

重庆城口地区下寒武统黑色岩系元素地球化学特征及其成因

地区广泛发育有下寒武统。利用ICP-MS方法系统分析重庆城口地区下寒武统黑色岩系中多金属富集层、炭质粉砂岩以及硅质岩样品的微量元素、稀土元素组成。研究结果表明稀土总量为111.41×10-6~184.13×10-6,平均为138.83×10-6,相对其他地区黑色岩系较低;LREE/HREE=2.49~3.44,LREE相对富集,HREE亏损;δCe=0.39~0.46,Ce呈明显负异常;δEu=0.84~1.10,Eu异常不明显。δCe,δU,V/Cr,Ni/Cr,V/(V+Ni)表明该区黑色岩系形成于缺氧环境;稀土元素地球化学特征及其相关图解、Cr,Sb,As,Bi的富集以及U/Th等反映本区黑色岩系非正常海水沉积产物,明显受热水沉积的影响,同时还存在火山活动的影响,火山活动可能为热水活动提供了动力及物质成分。     

修武盆地下寒武统黑色岩系铀矿物赋存特征及富集机理

通过野外地质调查、岩相学、地球化学和电子探针等分析方法,初步查明了修武盆地下寒武统黑色岩系中的铀矿物主要为磷钙铀矿和含磷钙钛铀矿,且多数以独立矿物形式存在,矿物颗粒微小,约1~3μm,少量与钛矿物共生;黑色岩系沉积受海底热液影响,其物源来自陆地和海底热水沉积物,由两者混合组成,且以陆源为主;铀的富集与碳、磷等元素关系密切。     

Mineralogy of Early Cambrian Ni‐Mo Polymetallic Black Shale at the Sancha Deposit,South China: Implications for Ore Genesis

The mineralogy of the Early Cambrian Ni–Mo polymetallic black shale ores at the Sancha deposit, South China, was investigated to better the understanding of the complex ore genesis by optical microscope, electron microprobe, and scanning electron microscope. Analytical results show that the sulfides in the ore bed mainly comprise C/MoS₂ mixed‐layer phase (MoSC), millerite, and pyrite. Of these, MoSC and millerite are the main ore minerals of Mo and Ni, respectively. Pyrite is subdivided into six types based on its morphology, occurrence, relationship to Ni‐ and Mo‐bearing minerals, and chemical composition. Many millerite crystals cut early‐formed MoSC, implying that these two minerals formed at different stages. The concentrations of biogenic elements (e.g., Sb) in the MoSC are high compared with those in millerite, implying a close relationship between MoSC and organic matter. These data provide a new and improved understanding of the complex ore genesis at the Sancha deposit, and can be applied to other black‐shale‐hosted mineral deposits worldwide.     

Metal sources for the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation,South China

Total organic carbon content (TOC), trace element and platinum-group element (PGE) concentrations were determined in the black shales of the Lower Cambrian Niutitang Formation in the Nayong area, Guizhou Province, South China, in order to study the polymetallic Ni–Mo–PGE mineralization. The results demonstrate that numerous elements are enriched in the polymetallic ores compared to those of the nearby black shale, particularly Ni, Mo, Zn, TOC and total PGE, which can reach up to 7.03 wt.%, 8.49 wt.%, 11.7 wt.%, 11.5 wt.% and 943 ppb, respectively. The elemental enrichment distribution patterns are similar to those in the Zunyi and Zhangjiajie areas except that the Nayong location is exceptionally enriched in Zn. Whereas positive correlations are observed between the ore elements of the polymetallic ores, no such correlations are observed in the black shale. These positively correlated metallic elements are classified into three groups: Co–Ni–Cu–PGE, Zn–Cd–Pb and Mo–Tl–TOC. The geological and geochemical features of these elements suggest that Proterozoic and Early Palaeozoic mafic and ultramafic rocks, dolomites and/or Pb–Zn deposits of the Neoproterozoic Dengying Formation and seawater could be the principal sources for Co–Ni–Cu–PGE, Zn–Cd–Pb, and Mo–Tl–TOC, respectively. Furthermore, the chondrite-normalized patterns of PGEs with Pd/Pt, Pd/Ir and Pt/Ir indicate that PGE enrichment of the polymetallic ores is most likely related to hydrothermal processes associated with the mafic rocks. In contrast, PGE enrichment in the black shale resembles that of the marine oil shale with terrigenous and seawater contributions. Our investigations of TOC, trace elements and PGE geochemistry suggest that multiple sources along with submarine hydrothermal and biological contributions might be responsible for the formation of the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation across southern China.     

铀的地球化学性质与成矿——以华南铀成矿省为例

铀是强不相容元素,随着岩浆演化而不断富集,在岩浆演化末期受结构氧增加影响进入独居石、磷钇矿等副矿物中。岩浆演化通常无法直接形成达到工业品位的铀矿床。铀是对氧逸度敏感的变价元素。在表生风化过程中岩体(层)中的铀被氧化为UO_2~(2+)而极易溶解进入水体中,并可在还原环境沉淀而富集成矿,氧化还原界面是找矿的理想选区。大气水可通过断裂构造系统进入一定深度,并受热源作用形成高氧逸度的热液而萃取出岩体(层)中的铀在还原位置沉淀富集形成矿床。新元古代氧化事件以及Marinoan冰期结束使得表生风化过程中更多的U进入水体;而寒武纪生命大爆发,易在沉积盆地底部形成还原环境,有利于U的沉淀富集。受上述三方面因素控制,在华南形成了广泛分布的富铀黑色页岩层,并被之后的沉积物覆盖,成为华南各型铀矿床的铀源层。印支期构造运动使部分富铀黑色页岩层发生部分熔融形成了富铀的S型花岗岩,该类岩石亦是之后铀成矿作用的铀源岩。燕山运动后期华南发生伸展构造背景下的岩浆热事件为以大气水为主的高氧逸度热液的形成并作用于铀源岩(层)提供了有利条件,促使华南各类型铀矿床开始在白垩纪集中形成。     

Genesis of tuff interval and its uranium enrichment in Upper Triassic of Ordos Basin,NW China

Recently measured high gamma ray values in the Yanchang Formation of the Upper Triassic in the Ordos Basin have added an interesting and controversial twist to the study of the formation’s uranium enrichment and genesis. High uranium and thorium contents in the tuffaceous layer cause high gamma ray values in the Yanchang Formation. Petrographic studies, major elements, rare earth elements (REEs), and trace elements have been systematically analyzed to determine the composition, geochemical environment, and diagenetic processes of the layer. The observed color of the tuffaceous layer in the study area varies from yellow to yellowish brown. The tuff consists of matrix supported with sub-rounded to sub-angular lithic fragments. These lithic fragments probably derived from pre-existing rocks and incorporated into the tuffaceous layer during volcanic eruption. Quartz, plagioclase, and biotite were observed in well to poorly sorted form, in addition to framboidal pyrite and organic laminae. Measured ratios of SiO₂/Al₂O₃ ranged from 3.277 to 6.105 with an average of 3.738. The ratio of TiO₂/Al₂O₃ varied from 0.037 to 0.201 with an average of 0.061, indicating that the sediments of the tuffaceous layer originated from an intermediate magma. REE distribution patterns show sharp negative Eu anomalies, indicating a reducing environment, which is suitable for uranium deposition. A reducing environment was confirmed by black shale in the base of the Yanchang Formation. Such black shale has high organic matter content that can take kerogene from mudstone and provide a reducing environment for uranium enrichment in the tuffaceous layer. Moreover, negative Eu anomalies and the REE patterns indicate a subduction-related volcanic arc environment as the magma source of the tuffaceous layers. High values of Rb, Ba, and Sr might be the result of fluid phase activities; low values of Hf and Eu indicate the involvement of crustal material during diagenesis of the tuff. Discrimination diagrams (Th/Yb vs Ta/Yb, Th/Hf vs Ta/Hf) suggest an active continental margin as the tectonic setting of source volcanoes. Plots of Nb versus Y, Rb versus Y + Nb, TiO₂ versus Zr, and Th/Yb versus Nb/Yb of the tuffaceous content point to calc-alkaline continental arc-related magmatism. We concluded that uranium enrichment in the tuffaceous layer was supported by oxidation–reduction.     

Seawater contribution to polymetallic Ni–Mo–PGE–Au mineralization in Early Cambrian black shales of South China: Evidence from Mo isotope,PGE, trace element,and REE geochemistry

The Early Cambrian black shale sequence of the Niutitang Formation in South China hosts a synsedimentary, organic carbon-rich, polymetallic sulfide layer with extreme metal concentrations, locally mined as polymetallic Ni–Mo–PGE–Au ore. In combination with previously reported data, we present Mo isotope, platinum-group element (PGE), and trace and rare-earth element (REE) data for the polymetallic sulfide ores and host black shales from four mine sites (Dazhuliushui and Maluhe in Guizhou Province, and Sancha and Cili in Hunan Province, respectively), several hundred kilometers apart. The polymetallic sulfide ores have consistently heavy δ^98/95Mo values of 0.94 to 1.38‰ (avg. 1.13 ± 0.14‰, 1σ, n = 11), and the host black shale and phosphorite have slightly more variable δ^98/95Mo values of 0.81‰ to 1.70‰ (n = 14). This latter variation is due to variable paleoenvironmental conditions from suboxic to euxinic, and partly closed-system fractionation in isolated marine sedimentary basins. Both the polymetallic sulfides and host black shales show PGE distribution patterns similar to that of present-day seawater, but different from those of ancient submarine-hydrothermal deposits and modern submarine hydrothermal fluids. The polymetallic sulfide bed has a generally consistent metal enrichment by a factor of 10⁷ compared to present-day seawater. PAAS-normalized REE + Y patterns of the polymetallic sulfide bed are characterized by a remarkably positive Y anomaly, consistent with an origin of the REE predominantly from seawater. Small positive Eu anomalies in some of the sulfide ores could reflect minor hydrothermal components involved. The Mo isotope, PGE, and trace and rare-earth element geochemical data suggest that metals in the polymetallic Ni–Mo–PGE–Au sulfide ore layer were scavenged mostly from Early Cambrian seawater, by both in-situ precipitation and local re-deposition of sulfide clasts.     

江西相山铀矿田深部多金属矿化中黄铁矿微量元素地球化学特征

在对相山铀矿田的深部勘查过程中陆续发现了一批铅、锌、银、铜多金属矿化,利用ICP-MS方法对多金属矿化中的重要金属矿物黄铁矿进行了微量元素分析。结果表明,黄铁矿中富集Co、Ni、Cu、Zn、Cd、Sb、Tl、Pb、Bi等微量元素。对比黄铁矿与矿区出露的主要岩浆岩和基底变质岩的LREE/HREE、(La/Yb)N、Y/Ho、Zr/Hf和Nb/Ta特征参数,结果表明多金属成矿流体在上升运移过程中受到变质基底的强烈混染。LREE富集,Hf/Sm、Nb/La和Th/La值小于1的特征表明多金属矿化成矿流体并非为富F流体,与铀成矿流体具有较大差异。微量元素Co含量与Co/Ni特征值显示矿化形成于中低温环境,成矿物质主要来自于基底变质岩。     

Geochemical Characteristics and Genetic Significance of Datangpo‐Type Manganese Ore Deposits during the Cryogenian Period

The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al₂O₃ and TiO₂, SiO₂, K₂O, and Na₂O, and strong negative correlations between Al₂O₃ and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K₂O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ¹³C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO₃^? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter.     

Geochemistry of soils derived from black shales in the Ganziping mine area, western Hunan, China

The geochemistry of major and trace elements (including heavy metals and rare earth elements) of the fresh and weathered black shales, and the soils derived from black shales in the Ganziping mine area in western Hunan province (China) were studied using the following techniques: X-ray fluorescence (XRF), inductively coupled plasma mass spectrometer (ICP-MS) and X-ray diffraction (XRD). The results show that the black-shale soils are significantly enriched with Al₂O₃ and Fe₂O₃, and depleted of mobile elements CaO, Na₂O and K₂O. The soils are also highly enriched with heavy metals U, V, Ni, Ba, Cu, Zn and Pb, that may cause potential heavy-metal contamination of the soils. Composition of the soils is homogeneous compared to the weathered black shales, for which the concentrations of major elements except CaO and Na₂O, and trace elements except heavy metals (U, V, Ni, Ba, Cu, Zn and Pb) as well as the mobile Sr, show lower variations than in the weathered black shales. Ratios of Zr/Hf, Ta/Nb, Y/Ho, Nd/Sm, and Ti/(Ti + Zr), of the soils are also less variable, with values constantly similar to that of the fresh and weathered black shales correspondingly. Thus, components of the soils are believed to be contributed from the parent black shales through weathering and pedogenesis. It is concluded that the soils were formed by at least two stages of geochemical processes: the early stage of chemical differentiation and the later stage of chemical homogenization. The chemical differentiation that was taken during black-shale weathering might have caused the depletion of CaO and Na₂O, and the enrichment of Al₂O₃ and Fe₂O₃; while the chemical homogenization that was taken during pedogenesis led to the depletion of SiO₂ and K₂O, and to the further enrichment of Al₂O₃ and Fe₂O₃. The heavy-metal enrichment (contamination) of the soils was then genetically related to the enrichment of Al₂O₃ and Fe₂O₃ in the soils.     

基于LA-ICP-MS多元素成像技术的早寒武世磷结核成因研究

我国下寒武统底部广泛发育磷结核、磷块岩等富磷沉积,为早寒武世最为重要的化学标志层之一,也代表了隐生宙—显生宙转折期地球表层系统的重大变革。当前对磷来源和富集机制的解释不一。为进一步明确该时期富磷沉积的形成机制,本文利用激光剥蚀电感耦合等离子体质谱联用技术(LA-ICP-MS)对贵州金沙地区牛蹄塘组黑色页岩中的磷结核进行多元素原位微区成像研究。结果表明:磷结核中各元素富集情况清晰地记录了磷结核形成过程中微环境的变化趋势。其中,磷结核内部Ca、P共富集以及Si亏损,指示P富集缘于自生磷灰石生成,P则来自于有机质含氧或厌氧降解释放;Mn、Zn与P共富集于磷结核内部,指示结核形成时的底部水体为含氧水体;As、Mo、V等元素主要富集于围岩或黑色页岩,指示缺氧含H_2S水体形成终止了结核生长。本研究显示,LA-ICP-MS原位多元素成像技术能够获取微区内丰富的地球化学信息,并提供高精度可视化证据,未来将在地质勘探和古环境研究等领域得到更广泛应用。