贵州织金新华磷矿床首次发现独立的稀土矿物

产于晚震旦世和早寒武世的不少海相沉积磷矿床富含碘、稀土、钒、镍、钼等可综合利用的元素。贵州早寒武世梅树村组早期的沉积磷块岩以富含稀土元素为特征,查明其中稀土元素的赋存状态有重要的理论和实际意义。不少研究认为稀土元素主要是赋存于胶磷矿中,但由于缺少有力的实验证据,对于稀土元素在胶磷矿中的具体存在形式,仅从理论上推测稀土元素是以类质同象的形式存在。最近,我们利用电子探针对贵州织金新华磷矿稀土元素赋存状态进行研究,在胶磷矿中发现了独立的稀土矿物———方铈矿。织金新华磷矿产于早寒武世梅树村及筇竹寺阶底部含磷岩…     

贵州织金磷矿床中离子吸附型稀土的存在及初步定量

近年来研究表明贵州织金磷块岩矿床中伴生丰富的稀土主要以类质同象形式存在,其主要依据为稀土总量与磷含量的正相关性,而对独立稀土矿物与离子吸附型稀土两种赋存状态的认识目前仍然不清楚。本文通过利用电感耦合等离子体质谱(ICP-MS)稀土元素全分析、磷钼酸喹啉重量法磷分析、岩矿鉴定与实验室选矿试验等方法对该矿床中伴生稀土的赋存规律进行了研究。岩矿鉴定表明矿石中主要矿物成分为胶磷矿并含少量黏土矿物,但未发现独立的稀土矿物;磷与稀土全分析显示稀土总量及各分量都与磷含量呈正相关,从而验证并进一步表明了稀土主要以类质同象形式存在于胶磷矿中。通过研究原矿经选别后稀土与磷在精矿、尾矿和选液(尾矿水)中的分配对比及两者的含量关系来探讨稀土的赋存规律,结果显示磷仅分配于精矿和尾矿中未发生损失,而11.98%的稀土在强电解质硫酸盐的作用下从原矿中解离出来进入了选液,推断这部分稀土在原矿中未进入矿物晶格,而是呈离子态吸附于矿物表面,初步认为漫长时限与潮湿条件下的充分风化作用以及胶磷矿与黏土矿物所充当的吸附载体发挥了作用,表明织金磷矿中稀土总量的11.98%以离子吸附状态存在。综合各分析结果,织金磷矿伴生稀土各赋存状态中类质同象占主导,未发现独立稀土矿物,而离子吸附型稀土占一定的比例,故将稀土的离子吸附形式列为仅次于类质同象的第二大赋存状态。     

高镁磷尾矿的矿石结构与矿物组成

利用电子探针背散射电子成像分析和微区成分分析功能,对贵州瓮福高镁磷尾矿的矿石结构和矿物组成进行了研究,以探索尾矿与其原矿之间的差异,为综合开发利用磷尾矿提供必要的依据。结果表明该高磷尾矿的矿石结构可分为单矿物结构和多矿物碎屑结构两类。前者矿物组成包括白云石单矿物、磷灰石单矿物、褐铁矿单矿物、石英单矿物;后者包括白云石-磷灰石多矿物、磷灰石-白云石-石英多矿物,属高镁低品位磷矿。矿物组成类型按其含量从高到低依次为白云石质尾矿、白云石磷灰石质尾矿、磷灰石白云石石英质尾矿、石英质尾矿、磷灰石质尾矿、褐铁矿质尾矿,白云石质尾矿是尾矿中最丰富的矿物,白云石颗粒是含量最高的碎屑类型。     

昆阳磷矿中稀土元素赋存状态研究

对昆阳磷矿中稀土元素的赋存状态进行了系统研究,结果表明矿体中稀土元素总量在50×10-6～250×10-6之间,以轻稀土元素富集、重稀土元素亏损为特征,Y含量在30×10-6～155×10-6之间,稀土元素总量与胶磷矿含量呈正相关关系。重砂矿物查找结果显示,昆阳磷矿中缺乏独立的稀土矿物。物相分析结果表明,稀土元素主要赋存在胶磷矿中,碳酸盐相和硅酸盐相中稀土元素含量极低。LA-ICPMS测试结果表明,胶磷矿单矿物中稀土元素总量在280×10-6～420×10-6之间,而白云石单矿物中的稀土元素总量均低于10×10-6。综合分析结果表明,昆阳磷矿中的稀土元素应主要以类质同像的形式存在于胶磷矿中。     

贵州省织金县打麻厂矿区含稀土磷矿中稀土元素赋存规律

为了定量查明贵州省织金县打麻厂矿区含稀土磷矿中稀土元素赋存规律,选取矿区具有充分代表性的样品,采用化学分析、ICP-MS分析、MLA分析、显微镜分析、单矿物分析、能谱分析、X射线衍射分析、扫描电镜分析等多种分析测试手段对样品进行分析检测。结果表明,矿区钇、镧、铈、钕4种稀土氧化物占稀土氧化物总量的82.97%,为高钇轻稀土。87.015%的稀土赋存在胶磷矿中,赋存在白云石、石英等硅质矿物、粘土类矿物、黄铁矿等矿物中的稀土分别占稀土总量的8.478%、2.604%、1.365%、0.367%。首次发现独立矿物磷铝铈矿和含稀土矿物磷铝锶石,以独立矿物形式存在的稀土仅占稀土总量的0.1047%,赋存在磷铝锶石中的稀土占稀土总量的0.0646%。赋存在胶磷矿和白云石中的磷的比例明显高于稀土,而赋存在石英等硅质矿物、粘土类矿物、黄铁矿、稀土独立矿物以及磷铝锶石中的稀土则显著高于磷。磷与稀土含量的相关系数R=0.9095,呈正相关关系。     

贵州织金磷块岩型稀土矿与热液作用:流体包裹体证据

对织金磷-稀土矿果化矿段中摩天冲、戈仲伍矿段中磷肥厂磷块岩进行岩相学研究,对磷块岩中石英、白云石矿物流体包裹体进行冷热台显微测温研究,结果表明,磷肥厂硅质磷块岩中胶磷矿主要以碎屑磷灰石形式存在,粒径50～200?m,以硅质胶结和白云石胶结为主;石英、白云石捕获流体包裹体均一温度分布于87.5～127.8℃,盐度变化于12.31%～20.61%,计算的流体压力为5.54～8.02 MPa;而摩天冲白云质磷块岩中胶磷矿主要以是碎屑磷灰石形式存在,粒径变化于50～300?m范围,以白云石胶结为主;白云石捕获的流体包裹体均一温度变化于99.8～184.3℃范围,盐度变化于12.31～20.61 wt%,计算的流体压力变化于13.7～22.6 MPa。碎屑磷灰石胶结物以及流体均一温度和盐度上存在显著的差异,指示果化矿段中摩天冲白云质磷块岩所揭示的热液体系很可能是热卤水与正常海水混合所致,而晚期不含NaCl的硅质热液对早期形成的白云质磷块岩的交代对戈仲伍矿段中磷肥厂硅质磷块岩有着重要的影响。     

磷矿综合利用研究

自然界中部分磷矿床,尤其是氟磷灰石矿床伴生大量稀土。贵州织金新华含稀土磷矿床就是非常具有工业价值的集磷矿产与稀土矿产于一体的超大型综合矿床。由于稀土离子与钙离子性质很相近,稀土主要以类质同象方式赋存于磷酸盐矿物中,因此分选富集磷矿时,稀土也富集到磷精矿中,具有很大的回收价值。为此针对贵州织金含稀土磷矿开发利用的需要,用织金磷矿浮选精矿为原料,模拟传统的二水法工艺制磷酸过程,并研究改善稀土溶解性能的方法,回收稀土元素及磷元素。     

云南安宁磷矿中稀土元素分布规律和赋存状态研究

磷矿伴生稀土元素是获取稀土资源的重要途径。我国磷块岩型稀土矿分布广,稀土含量高,具有综合回收价值,是仅次于独立稀土矿床的伴生稀土资源。本文主要研究云南安宁磷矿中稀土元素分布规律和赋存状态,并比较了磷矿石中稀土元素总量与磷含量的关系,结果表明磷矿石中稀土氧化物总量为72×10^-6～1 050×10^-6,与磷含量呈一定的正相关关系。另外通过光学显微镜及电子显微镜观察发现,安宁磷矿中缺乏独立的稀土矿物,只在部分海绿石中找到了独立的稀土矿物(可能为独居石和褐帘石)。LA-ICP-MS分析结果表明,胶磷矿单矿物稀土元素含量在770×10^-6～920×10^-6之间,而白云石单矿物稀土元素含量均低于34×10^-6,石英单矿物的稀土元素平均含量为180×10^-6。由于部分独立的稀土矿物的存在,海绿石矿物中稀土元素总量可高达2 947.27×10^-6～3 159.87×10^-6。综合分析结果表明,安宁磷矿中稀土元素主要以类质同像的...     

贵州织金新华含稀土磷矿床稀土元素地球化学及生物成矿基本特征

对贵州织金新华含稀土磷矿床进行的稀土元素及微量元素分析结果表明，磷块岩中普遍富集稀土元素，稀土总量∑REE较高，并富集Y元素及La，Nd等轻稀土元素。LREE／HREE比值较高。含稀土磷块岩普遍具Ce负异常，显示其对源区的继承性。指示成磷环境处于氧化程度相对较高状态。稀土元素球粒陨石标准化模式曲线、北美页岩标准化模式曲线、Ce元素异常、LREE／HREE比值、微量元素特征及岩石矿物特征表明，织金新华含稀土磷矿床具以正常海相生物-化学沉积等为主伴有海相热水沉积混合成因的特征。在磷矿成矿过程中沉积物沉积时，活体生物及死亡残骸不同程度地摄取和富集了La，Nd，Ce等稀土元素、Y元素及其他微量元素，沉积在含磷层位，构成大量的含稀土、含生物碎屑白云质磷块岩。     

织金新华磷矿碎屑磷灰石的矿物成分研究

织金新华磷矿是我国扬子地台西南缘早寒武世重要的海相沉积磷矿床.长期以来,织金磷块岩磷酸盐矿物成分被认为是碳氟磷灰石或低碳氟磷灰石,有学者认为,产于沉积岩中的磷灰石基本上都属于碳氟磷灰石.本文利用电子探针的微区成分定量分析技术和x射线衍射分析技术,确认织金磷矿碎屑磷灰石为氟磷灰石.     

Rare earth elements in supergene phosphorites

An analysis of rare earth elements in various types of supergene phosphorites established the following sequence of increasing average total contents (ppm): phosphorite from Christmas Island in the Indian Ocean, 3.89; spelean coprolitic phosphorite, 21.98; phosphorite from the weathering zone of sedimentary rocks, 27.41; phosphorite from the weathering zone of endogenous rocks, 372.32; and lacustrine coprolitic phosphorite, 461.59. Supergene phosphorites, especially the most common among them from the weathering zone of sedimentary rocks, are significantly depleted relative to marine phosphorites both in average and maximum REE contents. The REE contents of supergene phosphorites are controlled by several factors, including the REE contents in the primary rocks affected by weathering, the physicochemical conditions of phosphorite formation, the presence of a biogenic component in the phosphatogenetic system, and the structural type of the phosphorites. There is a strong positive correlation within the group of light and, in part, middle REEs (La, Ce, Nd, Sm, and Eu) and between the heavy REEs Yb and Lu, whereas the correlation between these two groups is weaker or insignificant. Gd and Tb are well correlated with the elements of both groups.     

江苏省海州式磷矿岩石地球化学特征及成矿背景

本文对苏北地区锦屏组磷矿石及地层样品进行了岩相学及地球化学分析,研究了磷矿初始沉积环境和源区特征。磷矿类微量元素富集Ba、Pb、U、Sr,贫Th、Ta、Nb、Ti;REE配分曲线为LREE富集型,Ce负异常,表明成矿环境为陆缘海,且成矿过程受深海热水沉积和生物作用影响。Sr、Nd同位素初始值判断磷灰岩物质来源为年轻的地壳物质。绿片岩类微量元素富集Rb、Th、K,贫Th、U、Ta、Nb、Sr、Ti;REE配分曲线为LREE富集型,判断其原岩为陆源碎屑岩。（混合）片麻岩类微量元素富集Pb、Th、K,亏损Ba、Ta、Nb、Sr、Ti;REE配分曲线为LREE富集型,具地幔源区特征。     

A comparative study of Pleistocene phosphorites from the continental slope off western India

Two types of phosphorite recovered from the continental slope off western India are described. The first type, phosphorite 1, comprises a hard, grey nodule composed of carbonate fluorapatite (CFA) and calcite as major minerals. The phosphorite consists of light‐brown microcrystalline apatite containing a few skeletal fragments and planktonic foraminifera. Scanning electron microscope (SEM) studies show evidence of dissolution of skeletal calcite and filling of the resulting cavities by phosphate composed of ovoid to rod‐shaped apatite microparticles. Apatite also occurs as coatings on these particles. The P₂O₅ content of the phosphorite is 29%, and the CO₂ content of the CFA is about 4·5%. The rare‐earth element (REE) abundance (ΣREE=2·02 μg g^–1) is lower than in other modern phosphorites. The ⁸⁷Sr/⁸⁶Sr ratio and ?Nd value of this sample are 0·70921 and –9·9 respectively. The ¹⁴C age found through accelerator mass spectrometry (AMS) dating (18 720 ± 120 years BP) is much younger than that determined by the U‐series method (100 ka). The second type, phosphorite 2, comprises a friable, light‐brown nodule consisting of CFA as the only major mineral, with a CO₂ content of the CFA of 4·5%. In thin section, the phosphate is light brown and homogeneous, and a few bone fragments are present. The P₂O₅ content is 33%, and REE contents (ΣREE = 0·18 μg g^–1) are lower than in phosphorite 1. The age of phosphorite 2 is >300 ka. Phosphorite 1 appears to have formed during the late Pleistocene through replacement of carbonate by phosphate; phosphorite 2 is also of Pleistocene age but is much older than phosphorite 1. The initial substrate for phosphorite 2 was a fish coprolite, which was subsequently phosphatized during slow sedimentation under low‐energy conditions. Microbial mediation is evident in both phosphorites. The colour, density and P₂O₅ content of the phosphorites are found to be dependent on the nature of the initial substrates and physico‐chemical conditions during phosphatization. The CO₂ content of the CFA is not related to the precursor carbonate phase. The nature of sediments, rates of sedimentation and the time spent undergoing phosphogenesis at the sediment–water interface may control REE concentrations in phosphorites.     

Application of LA-ICP-MS to sedimentary phosphatic particles from Tunisian phosphorite deposits: Insights from trace elements and REE into paleo-depositional environments

Laser ablation ICP-MS was used to determine trace (TE) and rare earth element (REE) contents of sedimentary phosphatic pellets and coprolites collected from late Paleocene-early Eocene phosphorite deposits in Tunisia. TE and REE contents in the investigated deposits exhibit a close relationship with grain types and paleogeography. Phosphatic pellets seem to concentrate more TE and REE than co-existing coprolites. Both particle types display modern oxic-suboxic seawater patterns. In most coprolites, ∑REE, Y, Cr, Ni, Th, and V show an increase from core to rim, whereas Ba, Cd, Cu, and U abundances decrease from core to rim, reflecting adsorption processes during early diagenesis consistent with changing redox and productivity conditions.The northern basins (Sra Ouertane) within open marine and platform settings tended to be more oxic-suboxic with relative high organic matter flux, while the eastern basins (Jebel Jebs) and Gafsa-Metlaoui basin are characterized by semi-restricted situation associated with suboxic-oxic conditions. This result is consistent with previous reconstructions which suggest that phosphorites of northern basins had a more direct connection to the open ocean than those to the south and east of the emerged area.This study highlights the potential for using laser ablation ICP-MS as a tool to reconstruct phosphorite depositional paleoenvironments.     

黔中陡山沱期磷块岩成因的系统研究

黔中成磷区是中国南方陡山沱成磷期磷块岩矿床的重要组成部分。包括瓮福、开阳两个大型磷块岩矿床和若干中小型磷矿床。本文从磷的来源、沉积和富集3个方面系统地揭示了该区磷块岩的成因。稀土元素分析表明,磷可能来自同期海底火山喷发物。海洋地球化学、生物化学及磷块岩的组构研究证明,藻类生物的吸收和固定作用是磷质沉积的主要途径。磷的富集的多阶段、多因素的,经历不同的富集阶段(或方式)形成不同的磷块岩类型。     

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。     

Scandium geochemistry of phosphorites, Guizhou, Southwest China

Geochemical characteristics of scandium are described with respect to its source,evolution and correlation with REE as observed in Late Sinian and Early Cambrian phosphorites and tuffs in Guizhou.Gomparison of chondrite-nomalized REE patterns and some other parameters between the phosphorite and tuff shows that scandium and REE are most likely to have been derived from earlier or contemporaneous marine volcanics or tuffs,with no indication of genetic link to the purple shales,silstones and dolomites in the area.The conditions under which the Sc-bearin phosphorites were formed are discussed in the light of sulfur isotopes and Eh-Ph constrains.     

REE geochemistry of Early Cambrian phosphorites from Gezhongwu Formation at Zhijin, Guizhou Province, China

The Cambrian Gezhongwu Formation in Southwest China is the lowest Cambrian phosphorite unit. The Formation belongs to the Meishucun stage with small shelly fossils. Rare-earth element (REE)data from the Gezhongwu phosphorites of Zhijin documented the depositional conditions. The total REE concentrations are high in the Gezhongwu phosphorites, which are especially rich in yttrium. The PAASnormalized REE patterns of the Gezhongwu phosphorites are characterized by negative Ce anomalies and slight enrichment of MREE, as being hat-shaped. The hat-shaped patterns suggest that the REE originated from depositional environments rather than from subsequent diagenesis. The negative Ce anomalies indicate that the depositional environments are oxic. The positive Eu anomaly, the high total REE and the hatshaped REE pattern revealed contributions from the normal marine environment mixed with hydrothermal water to the REE budget of the Gezhongwu phosphorites.     

塔里木盆地西克尔萤石地球化学特征及成因讨论

通过对塔里木盆地西克尔地区萤石矿及赋矿围岩进行地球化学分析,探讨该区萤石矿成因。研究表明,萤石矿物稀土元素配分模式图表现出轻稀土元素相对富集,正铕异常特点;微量元素分析显示Eu、Sr、Ba具有相关性;Sr同位素比值与围岩相近。最终认为萤石矿成矿流体主要来自于加热的盆地卤水,微量（包括稀土）元素来自下伏地层及围岩,Ba、Eu、F等元素可能来自下寒武统硅质岩及磷块岩。