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。     

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.     

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。     

贵州瓮安磷矿陡山沱组地层元素地球化学特征

瓮安陡山沱组上磷矿层含有大量早期多细胞动物化石(瓮安生物群),而陡山沱组下磷矿层未发现该生物群,说明上下两个磷矿层体现了不同的沉积环境。上磷矿层的氧化还原敏感元素Mo,U,V含量较下磷矿层要低很多。底部白云岩层、下磷矿层和中部白云岩层,无Ce异常,而上磷矿层和灯影组白云岩层Ce为负异常。这些表明,瓮安陡山沱组地层形成的海水沉积环境由下部的缺氧环境向上部的氧化环境转变。     

扬子区震旦系磷块岩的化学类型及其地质意义

经过对磷块岩化学成分分析，结合矿物分析资料，将磷块岩分成４种化学类型：富磷酸盐型、碳酸盐型、硅质型及富铝型，并探讨了它们的成因及其与沉积环境的关系。磷块岩的化学类型与稀土元素的含量有关，但与稀土元素的组成无关。轻重稀土元素的组成比值ＬＲＥＥ／ＨＲＥＥ＞１反映形成磷块岩的物源主要来自于陆源物。不同地区有相对稳定的轻重稀土比值。     

贵州织金新华含稀土磷矿床扫描电镜研究

用扫描电子显微镜和Ｘ射线能谱仪等方法研究织金新华含稀土磷矿床矿物组成,结构特征及微量元素含量变化特征。通过ＥＤＡＸ能谱仪进行矿物成分分析,得出Ｙ２Ｏ３质量分烽与胶磷矿物密切相关的结论。对伴生矿物作了相关研究,初步探讨了稀土元素赋存状态及富集规律。     

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。