贵州织金含稀土磷矿床的Sm-Nd同位素年龄及其地质意义

为探讨贵州织金含稀土磷矿床的形成时间和成矿物源, 利用Sm-Nd同位素稀释法对该矿床磷块岩中6个小壳化石及胶磷矿样品进行了年龄测定.样品的质谱分析测试结果显示, 样品的147Sm/144Nd与143Nd/144Nd构成了一条相关性良好的线性等时线; 计算结果表明织金含稀土磷矿床具有533±22Ma的Sm-Nd等时年龄, ε_Nd (t) 值为-2.44~-2.77, 表明它们具有相同的成因和相近的形成时代, 本次测得年龄代表着真实的成矿年龄; 二阶段Nd的模式年龄为1313~1338Ma.结合前人对该矿床稀土元素地球化学的研究成果表明, 织金含稀土磷矿床的成矿物源有新生地幔物质组分的加入.      

Geochemical diagenetic trends during phosphorite formation – economic implications: The case of the Negev Campanian phosphorites,Southern Israel

Research on the Upper Campanian (Upper Cretaceous) Negev phosphorites (Mishash Formation), based on microprobe analyses, Fourier Transform Infrared spectroscopy, wet chemistry, microtextural (Scanning Electron Microscopy) studies and mineralogical analyses, together with quantified rates of sedimentation and P accumulation, enables the chemistry of these rocks to be better constrained across the Negev area and allows their suitability for the manufacture of P fertilizers to be better determined. Two phosphorite facies are differentiated: (i) a pristine phosphorite facies of low P content, more typical of basinal sections and (ii) a reworked, granular phosphorite facies commonly enriched in P, found predominantly near palaeo‐highs and forming most of the economic phosphates. The distribution of F/P₂O₅, CO₂/F, U(IV), Cd, Zn and other trace metals (Mo, Ni, Cr, Cu, V and Y), rare‐earth elements concentration, Ce and Eu anomalies and heavy rare earth elements enrichment, are controlled by these two facies. F/P₂O₅ in carbonate‐fluorapatite is much lower (0·090 to 0·107) in the pristine than in the reworked facies (0·107 to 0·120); in addition, the lower F/P₂O₅ in the pristine facies is coupled with: (i) higher Cd, Zn, Mo, Ni, Cr, Cu and V concentrations; (ii) a considerably reduced (< 10%) U(IV) fraction of total U; (iii) lower rare earth elements/P₂O₅ and Y/P₂O₅ ratios; (iv) less negative Ce and Eu anomalies and lower heavy rare earth elements (Lu/La) enrichment; (v) an increase in Fe‐rich smectites in the clay fraction; and (vi) presence of OH in the carbonate‐fluorapatite structure. Sedimentary reworking of previously formed pristine phosphate, together with its redeposition near structural highs in more oxic bottom conditions, results in considerable diagenetic changes in the chemistry of the phosphorites, making them more suitable for economic exploitation. The results presented here provide geochemical criteria for identifying pristine phosphate in other phosphorite sequences and may help to better locate phosphate strata chemically suitable for the phosphate industry elsewhere.     

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。     

川滇黔相邻区古陆相沉积型稀土的发现及意义

文章报道了一种在川滇黔相邻区新发现的古陆相沉积型稀土矿床。稀土矿体赋存在二叠系峨眉山玄武岩之上,上二叠统宣威组底部,含矿建造为一套以高岭石及伊利石为主的黏土岩建造,分布广泛,连续性好,稀土氧化物TREO平均品位0.39%,最高可达1.60%。岩相古地理条件及地球化学特征显示,稀土元素源自西侧剥蚀区,经搬运-沉积-改造后富集;赋存状态方面,古陆相沉积型稀土除独立矿物态（<1%）,类质同象态（<1%）和离子吸附态（0.02%~24%）外,75%以上的稀土元素以纳米矿物颗粒的形态被“束缚”在黏土矿物层状结构中;稀土元素配分曲线图显示其高价值关键稀土元素镨、钕、铽、镝占比累计达23.34%;通过短流程的选冶一体化工艺技术,全元素稀土浸出率达到90%以上,综合回收率达80%以上。这一新类型稀土资源具有极大的开发利用前景,有望成为中国新的关键稀土元素来源。     

Phosphorites,glass ramps and carbonate factories: The evolution of an epicontinental sea and a late Palaeozoic upwelling system (Phosphoria Rock Complex)

The Permian Phosphoria Rock Complex of the western USA contains an enigmatic assemblage of bioelemental rocks (i.e. phosphorites and cherts) that accumulated in a depositional system with no modern analogue. This study utilizes detailed sedimentological, stratigraphic and petrographic examination to evaluate the genetic relations of phosphorites, spiculitic chert and carbonates of the Ervay cycle (depositional sequence) and propose a unified oceanographic model for their deposition. The Ervay cycle contains three marine and one terrestrial facies association, each of which composes the bulk of a single lithostratigraphic unit. The marine facies associations include: (i) granular phosphorites (Retort Member); (ii) spiculitic cherty dolostones (Tosi Member); and (iii) marine to peritidal carbonates (Ervay Member). Red beds and intercalated gypsum (Goose Egg Formation) accumulated in the vast desert adjacent to the sea. The three marine members are chronostratigraphically distinct, successive and conformably stacked. They are not coeval facies belts. They reflect the progressive evolution of the epicontinental sea from the location of: (i) authigenic phosphogenesis (lowstand to transgression); to (ii) a glass ramp with biosiliceous (sponge) deposition (transgression); to (iii) a carbonate ramp (regression). This succession of switching biochemical sediment factories records the evolution of sea-level, nutrient supply, upwelling, oxygenation and dissolved Si. Intense upwelling, potentially coupled with aeolian input, led to sedimentary condensation and phosphogenesis. Decreased upwelling intensity during transgression increased oxygenation sufficiently for a siliceous sponge benthos. Sponges were favoured over biocalcifiers due to elevated dissolved silica and a low carbonate saturation state. The cessation of sponge dominance and transition to a carbonate ramp occurred due to decreasing upwelling intensity, Si drawdown and an increased carbonate saturation state. These results provide insight into the role of Si loading in faunal turnover on glass ramps and highlight how differences in dissolved Si utilizers in pre-Cretaceous versus post-Cretaceous upwelling systems influence the resultant deposits.     

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.     

湖北省放马山磷矿物质组分及元素地球化学特征

湖北省放马山磷矿层位为震旦系陡山沱阶。在对其第一磷矿层(Ph1)和第三磷矿层(Ph3)物质组成、结构、构造等研究的基础上,对比Ph1和Ph3的化学分析数据,Ph1的I、Sr、Ba和Cd含量相对富集,表明其形成与有机质和微生物作用关系比Ph3更大。采用Co/Ni、Th/U来做相近元素的比值分析,Co/Ni值小于1、Th/U值大于1,在logw(U)-logw(Th)关系图中,Ph1和Ph3磷块岩样品点几乎都落在热水沉积区,表现出热水沉积成因的地球化学特征。稀土元素的北美页岩标准化配分模式图呈宽阔的帽状图形,并显示明显的Ce负异常,反映在正常的海相沉积过程中有海相热水流的加入。     

中国磷矿床成因分类

中国磷矿床按成矿物质来源,划分为内源、外源及次生三大类。按基本的成矿作用,将原生矿床分为岩浆、沉积、变质类型。岩浆矿床中,划分为超基性-碱性岩、超基性-碳酸岩、碱性岩、碳酸岩、超基性岩、伟晶岩等7个亚类,据总体的矿床特征划分为6个式(矿床式多以典型矿床命名)。变质矿床中划分绿岩带型变质混合岩和沉积变质3个亚类,6个式。海相沉积磷块岩矿床依据产出时代划分出震旦纪、寒武纪、泥盆纪3个亚类,14个式。次生矿床分为风化淋滤残积、洞穴堆积及鸟粪堆积3个亚类,3个式。     

贵州织金新华含稀土磷矿床矿区土壤稀土元素分布特征

稀土元素分析结果表明,贵州织金新华含稀土磷矿床矿区上层土壤中普遍富集稀土元素．其∑REE较高,但比含稀土磷块岩低．表明磷块岩在风化过程中已有部分稀土元素流失。轻稀土元素La、Ce及Y大量集中,LREE／HREE比值较高,说明岩石在风化过程中形成的粘土矿物对稀土元素有一定的吸附作用。但是粘土矿物对稀土元素的吸附量小于REE易溶配合物的流失量。稀土元素球粒陨石标准化模式曲线及Ce异常等特征表明,织金新华含稀土磷矿床矿区土壤中稀土元素分配模式继承了原岩特征。     

江西德兴斑岩铜钼矿床流体包裹体子矿物SEM-EDS 研究及其对成矿流体性质的制约

江西德兴斑岩铜钼矿床Q+Py±Cp±Cc脉、(黄铁)绢英岩和Q+Py+Mo±Cp脉中发育大量多相(透明、暗色子矿物)包裹体。本文以详细的显微观察和流体包裹体岩相学观察为基础,利用SEM-EDS(扫描电镜-X射线能谱仪)对多相包裹体内的子矿物进行了系统的鉴定。分析结果表明,Q+Py±Cp±Cc脉石英中发育的透明子矿物包括绢云母、石盐、水氯镁石、白云石、铁氯化物、磷灰石和含稀土元素磷酸盐;暗色子矿物包括赤铁矿、铁氧化物和黄铜矿。(黄铁)绢英岩石英和黄铁矿中透明子矿物包括石盐、(硬)石膏、绢云母、硫酸镁、菱镁矿、六水泻盐和(Fe、Cu、Mg)碳酸盐和硫酸盐,暗色子矿物包括磁铁矿、赤铁矿、金红石和黄铜矿;Q+Py+Mo±Cp脉石英包裹体中发育的子矿物相对较少,透明子矿物包括石盐、菱铁矿和钾长石;暗色矿物为赤铁矿。它们中发育种类繁多的子矿物,表明热液的化学成分非常复杂,多种盐类以及高氧化态子矿物出现指示流体具有高盐度-高氧化态的特征。此外,还鉴别出了黄铜矿、赤铁矿和磁铁矿等金属矿物,这表明热液含有丰富的成矿物质,这些成矿物质随物理化学条件的变化以黄铜矿等金属矿物从热液中沉淀下来,形成了矿床内的主要矿体。结合蚀变矿物组成观察,我们认为Q+Py±Cp±Cc脉、(黄铁)绢英岩和Q+Py+Mo±Cp脉中子矿物组成很可能不代表原始流体的化学成分,因为它们在很大程度上受到了热液蚀变作用的影响,围岩矿物由于水-岩反应被分解,同时释放出Na、Ca、Mg、Fe等元素进入热液,形成了上述种类多样的子矿物。通过流体包裹体岩相学观察发现,(黄铁)绢英岩和中Q+Py+Mo±Cp脉含石盐多相包裹体通常与富气包裹体或者CO₂包裹体紧密共生,这表明热液在被捕获前发生了相分离(或沸腾)作用,而这一过程必然会导致富液包裹体盐度的升高,因此不能排除这些高盐包裹体是由中低盐度流体发生相分离而形成的可能性。Q+Py±Cp±Cc脉中发育的稀土子矿物指示成脉流体具有高盐度-低pH-含CO₂的特征,而这类子矿物在(黄铁)绢英岩和Q+Py+Mo±Cp脉中不发育的原因可能是CO₂与液相发生了相分离作用。