贵州瓮福新元古代陡山沱期磷矿床铅同位素特征及来源探讨

贵州新元古代陡山沱期瓮福磷矿下矿层条纹-条带状磷块岩的磷条带、泥岩条带、上矿层磷块岩的磷质、白云质胶结物有各自不同的铅同位素组成特点。在Zartman铅构造模式图解中，下矿层磷条带和泥质磷块岩条带位于地幔铅、造山带铅和上地壳演化线之间，并呈很好的线性关系。上矿层块岩的白云质胶结物远离所有类型铅的演化线。下矿层的泥岩条带位于幔源铅和上志壳铅演化线之间，但与磷质不同，更偏向于白云质胶结物的分布区。在朱炳泉等（1998）的△γ-△β铅来源分类图上，上矿层和下矿层的甩磷质样品分布于地幔铅、上地壳与地幔混合俯冲带碎屑沉积作用铅和海底热水作用铅区。上矿层磷块岩的白云质胶结物分布于上地壳和地幔混合俯冲带岩浆作用铅、化学沉积型和海底热水作用型铅区。泥岩条带分布于地幔源和海底热水作用型铅区。因此，瓮福磷矿磷质样品的铅主要具地幔铅、上地壳铅和热水沉积作用的混合来源，以地幔为主。上矿层白云质胶结物铅同位素具有海源和海底热水作用的混合来源。下矿层泥岩条带铅同位素具地幔、上地壳和海源铅的混合特点。陡山沱期大规模磷质成矿的初始物质主要来源于地幔，预示着磷质的超常成矿与磷质生物的爆发可能与地幔体制的变化有某种成因联系。     

贵州瓮安磷矿上震旦统陡山沱组地层和沉积环境

瓮安磷矿当时位于川黔滇台地东南边缘,是我国晚震旦世陡山沱期主要的磷矿之一。该区陡山沱组含磷地层中发现大量低等蓝藻和真菌、红藻、大型球状绿藻、疑源类及可能的后生动物化石,引起国内外地质学家和古生物学家的关注,尤其是最近报道从该地层中发现具细胞结构的海绵和动物胚胎化石,震动了各国古生物学界。瓮安磷矿的陡山沱组不整合于南沱组或板溪群之上,为灯影组浅灰白色白云岩层整合覆盖,以中部的古喀斯特侵蚀面为界而分为下、上两个岩性段,构成下段的白云岩—磷块岩—白云岩序列和上段的磷块岩—白云质生屑磷块岩—磷质白云岩序列。化石产于陡山沱组上段。     

贵州瓮安陡山沱组磷块岩的地球化学特征

贵州瓮安地区是震旦纪陡山沱期的一个磷块岩沉积区,生物作用是磷矿形成的重要因素。通过对贵州瓮安含磷岩系剖面地球化学特征的研究,认为磷块岩富集层是以P2O5与CaO构成的磷酸盐矿物为主,可分为白云质砂屑磷块岩和碳质磷块岩2个亚类;生物作用导致了磷块岩中Pb,As,Ba及Sr等微量元素的富集,其中亲硫元素Pb的含量最高达到1 446×10-6,反映了贵州瓮安震旦系陡山沱组磷块岩的成因与菌藻类生物作用密切相关。     

贵州瓮安陡山沱组磷块岩的稀土元素地球化学特征与沉积古环境

晚元古代末的陡山沱期(550-600Ma)是地球历史生物、化学和气候变化的剧烈时期。通过对贵州瓮安陡山沱组磷矿的稀土元素研究，确定上矿层磷块岩的北美页岩标准化稀土模式具负Ce异常、轻和重稀土亏损及中稀土富集特征。下矿层磷块岩稀土模式为轻微负Ce异常、轻微的轻和重稀土亏损及中稀土富集。下矿层磷块岩的Ceanom值为-0．065～-0．077，上矿层磷块岩的Ceanom为-0．26～-0．291，表明瓮安磷矿沉积古环境从下矿层的还原条件转变为上矿层的氧化条件。这种南沱冰期之后的环境变化可能为瓮安动物群的大爆发提供了必要的条件。     

贵州瓮安陡山沱组含磷岩系沉积序列及磷块岩的形成

贵州瓮安陡山沱组磷块岩为碳酸盐岩型含磷岩系,属于浅海碳酸盐岩台地沉积区。对瓮安磷矿大塘剖面进行沉积环境研究,将Marinoan冰期后沉积的陡山沱组地层分为6个向上变浅的沉积序列。瓮安含磷岩系大部分为多旋回的叠置体,其常见的交错层理、波状层理、透镜状层理等表明了磷块岩形成于水体较浅的高能环境。南沱冰期后,陡山沱期剧烈的海侵作用引发上升洋流,携带富磷海水涌入浅水区,在海平面间歇性波动的条件下,为磷块岩的形成提供了物源与动力条件。     

富磷矿三阶段动态成矿模式:黔中开阳式高品位磷矿成矿机制

震旦系陡山沱组沉积期形成的黔中开阳、瓮安富磷矿沉积区,矿石产量大、品位高,是国内外重要的磷矿资源产区。黔中磷矿主要分布于黔中古陆周缘的滨浅海环境中,矿石类型以碎屑状磷块岩为主,间夹原生泥晶磷块岩、生物结构磷块岩和次生土状结构磷块岩。开阳式高品位磷块岩的动态沉积成矿过程通常为“三阶段成矿”: 第一阶段为初始成磷作用阶段,在新元古代大规模成磷背景下,上升洋流携带深部富磷海水进入滨浅海地区,并通过生物化学作用使磷质聚集并形成原生磷块岩沉积;第二阶段为簸选成矿作用阶段,高能波浪、风暴水流对原生磷块岩持续的破碎、磨蚀、搬运和再沉积过程中,簸选去除了原生沉积物中的陆源细碎屑、砂泥质成分,保留并聚集磷质碎屑颗粒,形成品位较高的碎屑状矿石;第三阶段为淋滤作用阶段,海平面升降变化使之前形成矿石受暴露事件影响,遭受强烈的风化淋滤作用,碎屑状磷矿石内的碳酸盐岩胶结物和白云石条带被淋滤运移,导致矿层发育大量溶蚀孔洞,甚至形成土状磷块岩,矿石品位再次得到大幅度提升。三阶段成矿作用随古地理条件和海平面变化在沉积成岩过程中多期次、动态进行,最终形成工业价值极高的磷矿石。     

黔中开阳地区震旦纪陡山沱期富磷矿沉积特征与成矿模式*

黔中开阳地区在震旦纪陡山沱期全球成磷事件的大背景下,发育了厚度较大的富磷矿层。通过岩石薄片观察、地层对比与划分及沉积相分析等手段,探讨黔中开阳地区震旦纪陡山沱期磷矿床沉积特征与成矿模式。结果表明:(1)开阳地区陡山沱期处于黔中古陆北缘的磷质海岸环境,磷矿层中分布最广泛、品位最高的矿石类型为砂屑磷块岩,为富磷沉积物在沉积、成岩过程中遭受多期次冲刷破碎、暴露淋滤及堆积胶结的产物。(2)开阳地区古地理环境和动荡的海水条件控制了磷矿的沉积和高品位矿石的分布,洋水、永温等地在震旦纪陡山沱期所处的海水深度适中的临滨带为成矿优势地带,而水体过浅的前滨带和过深的远滨带均不利于磷质的聚集和成矿。(3)开阳地区动态磷矿床成矿模式表明,陡山沱期海平面的频繁进退使临滨带已沉积的磷块岩遭受多期次的冲蚀、暴露、淋滤、胶结及磷质再沉积作用;通过物理分选作用和风化淋滤作用最终使磷质聚集,是研究区富磷矿形成的主要原因。     

贵州震旦系陡山沱组磷块岩成磷作用及与新元古代末期氧化事件(NOE)的耦合*

新元古代末期历经“雪球地球”和大气、海洋增氧事件后,发生了全球性成磷事件,贵州省震旦系陡山沱组大规模磷矿床沉积是本次成磷事件的典型代表。然而现阶段对贵州陡山沱组磷块岩成磷作用机制研究存在诸多争议,成磷事件与同期古海洋环境转变之间的关联研究也较为薄弱。作者以贵州省瓮安、遵义和丹寨地区陡山沱组原生磷块岩为研究对象开展的沉积学、岩石学、矿物学和地球化学特征研究表明: 陡山沱早期成磷作用被限制在浅水海岸,瓮安地区A矿层球粒磷块岩中大量的含铁自生矿物黄铁矿、海绿石以及无Ce负异常指示的贫氧沉积水体环境均表明,Fe-氧化还原泵成磷模式在富磷过程中发挥了重要作用;陡山沱晚期磷块岩分布扩散至较深水陆棚—斜坡沉积相区,磷块岩与富有机质岩层共生,矿物晶体形态特征与矿石内富含的大量生物化石均表明,有机质沉降聚磷作用和生物成磷作用促使磷块岩大量沉积,较明显的Ce负异常值也指示了海水氧气含量的提升。成磷作用模式的转变和磷块岩分布的扩展是对海洋增氧事件的沉积响应,同时造成的多细胞动物演化也影响了深部水体的氧化还原状态,进而反映了贵州省陡山沱组磷块岩大规模沉积与新元古代末期氧化事件(NOE)密切的耦合关系。     

贵州瓮安陡山沱组磷块岩生物标志物特征及对沉积环境的指示

贵州瓮安新元古界陡山沱组磷块岩中发现的瓮安生物群主要包括多细胞藻类、蓝菌、疑源类、后生动物休眠卵及胚胎、管状后生动物和两侧对称的后生动物等化石类型。对瓮安陡山沱组磷块岩的有机地球化学分析表明,烃类有机组分包括正构烷烃、萜类、甾类和类异戊二烯烃。正构烷烃主峰为C21,碳数分布范围宽;OEP值为1．03,接近1。Pr／Ph比值为0．95,植烷略显优势。规则甾烷呈不对称的“V”字形分布,表现为C27〉C29〉C28的分布特征。C27占优势可能是由大量的带刺疑源类昕致。生物标志物特征指示瓮安陡山沱组磷块岩中的有机物来源于藻类和细菌,显示还原性、较高盐度的成磷沉积环境。     

震旦系陡山沱组Sm-Nd年龄测定

晚震旦世陡山挖期是南挖冰期后第一次生物爆发期，又是我国南方重要的磷、锰和重晶石等矿产形成期，是末前寒武纪的重要时期之一。最近，分别在贵州息峰温泉、开阳洋水沙坝土、福泉拦马坳、上饶朝阳王家院及贵州瓮安大塘等剖面，于陡山沱组顶部采集磷块岩和磷质样品，     

Rare earth elements in the sedimentary cycle: A summary

The relative and absolute concentrations of rare earth elements (REE) in authigenic and biogenic phases of deep-sea sediments are quite different. Competition between these phases for REE has resulted in fractionation from the parent material, the latter consisting predominantly of terrigenous material, but with a contribution from marine volcanism. The strongest feature of this fractionation is a depletion of Ce, relative to La, in CaCO₃, opalline silica, phillipsite, phosphorite, barite, and montmorillonitic clays; and a Ce enrichment in Fe/Mn nodules. The distribution of REE in different masses of seawater strongly reflects their fractionation in sediments. Whereas the relative concentration of REE in rivers resembles that of shale, their removal from seawater by authigenic and biogenic phases results in: (1) a decrease of their total concentration; (2) a depletion of Ce; and (3) an enrichment of heavy REE relative to light REE. The order of fractionation for water masses in the Atlantic Ocean is:Antarctic intermediate water > North Atlantic deep water > Antarctic bottom water> shelf water > river water ～ shale.The shale-normalized pattern for the sum of REE in the authigenic and biogenic phases of pelagic sediment and in seawater resembles that of an admixture of shale and basalt corresponding presumably to the realtive inputs from continents and marine volcanism respectively. The estimated rate of accumulation of each REE in the sediment, however, is approximately 12 times the estimated rate of input of REE from these two sources.     

贵州镇宁重晶石矿中硅质岩稀土元素地球化学研究

通过对镇宁泥盆系重晶石矿中硅质岩稀土元素地球化学特征研究,发现硅质岩稀土总量较低,轻稀土富集,δCe呈弱的负异常,δEu呈负异常到正异常,{La/Sm}N和{Gd/Yb}N值表明轻稀土分异强;通过∑REE、Ce/Ce＊、Eu/Eu＊、{La/Ce}N和{La/Lu}N参数综合分析,硅质岩沉积成岩过程中有明显的热水参与,...     

渝东南地区石牛栏组稀土元素地球化学特征及地质意义

渝东南地区的下志留统石牛栏组作为重要的油气储集层,研究其古环境变化、物质来源及物源区构造背景具有重要意义。本文采用稀土元素总量w(ΣREE)、REE配分模式、以及w(ΣLREE)/w(ΣHREE)、w(La)_N/w(Yb)_N、w(Ce)_N/w(Yb)_N、w(La)_N/w(Sm)_N、w(Gd)_N/w(Yb)_N、δEu、δCe、Ce_(anom)等特征值研究方法,对渝东南下志留统石牛栏组典型剖面的稀土元素特征及古海洋环境和物源进行深入研究。结果表明:石牛栏组灰岩稀土元素总量略低于大陆地壳平均值,轻稀土较为富集,重稀土亏损,铕明显负异常,铈负异常较微弱。w(ΣREE)证实了石牛栏组的沉积水体由浅缓慢变深再急剧变浅的变化过程。Eu负异常、Ce负异常和C_(eanom)值均揭示石牛栏组沉积时期海水具有弱还原性。REE的分异程度反映了石牛栏组从沉积早期到沉积晚期,沉积速率总体降低。稀土元素的比值特征及w(ΣREE)—w(La)/w(Yb)图解表明其物源源自雪峰山隆起,源岩主要为沉积岩。     

巴格毛德油页岩中稀土元素特征研究及其地质意义

油页岩中的稀土元素（REE）研究不仅可以用于解决岩石地质成因,提供物质来源信息,而且可以对REE含量进行资源评价,有利于油页岩的综合开发利用,具有重要的理论和现实意义。本研究测试并分析了银额盆地巴格毛德凹陷中生界白垩系下统巴音戈壁组（K1b）巴格毛德油页岩REE地球化学特征,分析结果表明,油页岩中的REE总量（∑REE）为94．8×10^-6～178×10^-6,平均值为126×10^-6,低于其围岩的∑REE;轻、重稀土元素含量比值（∑LREE／∑HREE）为2．60～3．45,平均值为3．10。（La／Yb）w为0．57～1．02,平均值为0．89,表明油页岩中LREE、HREE分异不明显,LREE相对HREE富集,属于LREE低度富集型。Eu表现为明显负异常,Ce表现为微弱的正异常,表明了油页岩形成于还原的古湖泊环境。油页岩样品∑REE与其微量元素的聚类分析结果表明,油页岩中的REE主要来自陆源碎屑沉积。油页岩样品δCe与δEu、δCe与∑REE均无明显的相关关系,表明成岩作用对REE的影响十分有限,研究区油页岩的成岩阶段处于未成熟阶段。     

鲕粒,豆粒磷块岩的显微结构和生成特点

晚震旦世陡山沱组和早寒武世渔户村组、辛集组磷矿中有各种鮞粒、豆粒磷块岩。豆粒、鮞粒内核的成分和结构复杂,有来自陆地的各种岩石砂屑、细砾,也有盆内沉积物破碎成的各种内碎屑。鮞粒、豆粒的壳层是同心纹层状磷灰石,它是内核在富磷海水扰动中逐层淀积而成。大部分豆粒、鮞粒在滨海高能浅水中与陆源砂、砾和岔内碎屑沉积在一起,少量鮞粒则沉积在滨外深水低能环境巾。豆粒、鮞粒和碎屑等沉积后又被不同物质胶结。     

Content and mode of occurrences of rare earth elements in the Zagrad karstic bauxite deposit (Nikšić area,Montenegro)

Three vertical sections through the Zagrad deposit of Jurassic karst bauxite in central Montenegro have provided knowledge of the vertical distribution of major and some selected trace elements, including rare earth elements (REE). Variations in the mineralogy, particularly those hosting REE, have been studied. This has revealed the presence of authigenic mineral phases such as xenotime, mottramite and monazite (best proved using Raman microprobe analysis) as well as residual phases such as zircon, titanite and monazite. The mobility of the elements during bauxitization processes has been studied to show that the REE minerals ensure progressive concentration of these elements during removal of major elements through weathering. The similarity of normalized REE in the bauxite to the typical Post-Archean Australian Shales (PAAS) and Upper Continental Crust (UCC) profile, and the preserved Eu anomaly, are evidence that the bauxite was not derived from carbonates and represents alteration of shale, marly limestone and volcanogenic or proximal igneous sourced detritus that accumulated in the original karst landform. Mass change during bauxitization, using Ti as “index” element and compared to PAAS composition, revealed almost 100% depletion of Si and weak enrichment in Al. Deeper parts of the deposit with authigenic minerals exhibit very strong enrichment in all REE. The bauxite ores have high ΣREE contents (693.5–6953.4 ppm), especially ΣLREE contents (582.8–4882.9 ppm), while ΣHREE contents (106.6–2070.5 ppm) are much lower.     

Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China: Their mobilization,redistribution, and fractionation

In this study, the mobilization, redistribution, and fractionation of trace and rare earth elements (REE) during chemical weathering in mid-ridge (A), near mountaintop (B), and valley (C) profiles (weak, weak to moderate, and moderate to intense chemical weathering stage, respectively), are characterized. Among the trace elements, U and V were depleted in the regolith in all three profiles, Sr, Nb, Ta, Zr, and Hf displayed slight gains or losses, and Th, Rb, Cs, and Sc remained immobile. Mn, Ba, Zn, Cu, and Cr were enriched at the regolith in profiles A and B, but depleted in profile C. Mn, Pb, and Co were also depleted in the saprock and fractured shale zones in profiles A and B and enriched in profile C. REEs were enriched in the regolith and depleted at the saprock zone in profiles A and B and depleted along profile C. Mobility of trace and REEs increased with increasing weathering intensity. Normalized REE patterns based on the parent shale revealed light REE (LREE) enrichment, middle REE (MREE), and heavy REE (HREE) depletion patterns. LREEs were less mobile compared with MREEs and HREEs, and this differentiation increased with increasing weathering degree. Positive Ce anomalies were higher in profile C than in profiles A and B. The Ce fractionated from other REE showed that Ce changed from trivalent to tetravalent (as CeO₂) under oxidizing conditions. Minimal REE fractionation was observed in the saprock zone in profiles A and B. In contrast, more intense weathering in profile C resulted in preferential retention of LREE (especially Ce), leading to considerable LREE/MREE and LREE/HREE fractionation. (La/Yb)_N and (La/Sm)_N ratios displayed maximum values in the saprock zone within low pH values. Findings demonstrate that acidic solutions can mobilize REEs and result in leaching of REEs out of the highly acidic portions of the saprock material and transport downward into fractured shale. The overall behavior of elements in the three profiles suggests that solution pH, as well as the presence of primary and secondary minerals, play important roles in the mobilization and redistribution of trace elements and REEs during black shale chemical weathering.     

六盘山盆地白垩系马东山组泥页岩稀土元素地球化学特征及地质意义

以六盘山盆地白垩系马东山组泥页岩为研究对象,通过稀土地球化学元素测试分析,结果表明六盘山盆地马东山组泥页岩REE为125.2×10^-6~175.1×10^-6,均值为153.4×10^-6,略低于北美页岩;∑LREE为114.4×10^-6~160.6×10^-6,均值140.2×10^-6,∑HREE值为10.78×10^-6~14.69×10^-6,均值13.26×10^-6;LaN/SmN、GdN/YbN、∑LREE/∑HREE及经标准化REE分布模式均反映出LREE相对富集且分异明显、HREE相对亏损且分异不明显。Eu明显负异常,Ce弱负异常,成岩作用对REE影响有限。REE配分模式显示马东山组泥页岩沉积物源较为一致,∑REE—La/Yb图解表明其母岩为沉积岩,负Eu异常说明该沉积岩母岩具有花岗岩物源特性。w(∑REE)与w(Al2O3)、w(SiO2)、w(TiO2)及w(CaO)相关性说明马东山组泥页岩REE受近源陆源碎屑供应、水体自身元素分异及生物作用共同控制。REE总量、Eu负异常、Ceanom、δCe、LaN/YbN等指标显示马东山组泥页岩沉积时期气候温暖湿润,泥页岩主要沉积于具有一定深度水体的氧化还原界面以下,沉积速率稳定且缓慢,为有机质的保存提供良好条件。     

苏鲁皖新生代玄武岩中巨晶组合的稀土元素特征

我国东部苏鲁皖地区新生代碱性玄武岩中,除了含有大量地幔橄榄岩类捕虏体以外,尚含有一定数量的石榴石、普通辉石和歪长石巨晶。这些巨晶是在地幔不同深度上从玄武岩中晶出的。巨晶组合的分离结晶作用对熔体稀土元素含量有很大影响。赋存巨晶的碱性玄武岩所具有的LREE富集、HREE亏损的稀土元素分配型式是由地幔橄榄岩类部分熔融程度、石榴石巨晶和普通辉石巨晶的早期高压熔离和玄武岩的结晶分异作用等综合因素造成的。