Diagenetic trends of fluorine concentration in Negev phosphorites, Israel: implications for carbonate fluorapatite composition during phosphogenesis

An electron probe and chemical study of bulk phosphorite samples and separated constituents from various Negev deposits was carried out together with XRD, FTIR spectroscopy and textural analysis. The results allow a better understanding of the distribution of fluorine in these Upper Cretaceous phosphorite sequences and shed light on variations in the composition of the carbonate fluorapatite (CFA) phase during phosphogenesis. Two facies are recognized: (1) a pristine, microbially generated phosphorite facies; (2) a recycled, peloidal and biodetrital facies. Fluorine distribution in the Negev phosphorites is facies controlled: F/P₂O₅ is much lower in the pristine facies (0·090–0·107) than in the recycled facies (0·107–0·120). In addition, F/P₂O₅ varies considerably between the various constituents of the phosphate fraction; F‐poor francolites (F/P₂O₅ as low as 0·080) co‐exist with F‐rich francolites (F/P₂O₅ as high as 0·135) in the same phosphorite bulk sample. A lower F/P₂O₅ in francolite is associated with higher Cd and Zn concentrations in the phosphorite, an increase in Fe‐rich smectites in the clay fraction and the presence of structural OH in the francolite. The lower F/P₂O₅ ratios in the pristine facies are attributed to high organic deposition rates during the formation of these matted sediments, leading to rapid burial of the in situ‐forming CFA. This is possibly coupled with diffusion of F from sea water into bottom sediments being hampered by microbial mat coatings. These conditions resulted in O₂‐depleted porefluids, inducing the precipitation of Cd‐rich Zn sulphides and the formation of Fe‐rich smectites. F‐enrichment probably takes place when the earlier formed F‐poor ‘primary’ CFA is relocated close to the sea floor and bathed with interstitial sea water solutions of higher F concentrations. Oxidation and removal of the sulphide‐bound Cd and Zn apparently occurred together with enrichment in F of the francolite. Combining chemical data with XRD and FTIR results suggests a multistage growth for the Negev phosphate constituents in shifting formational sites and porefluids of varying F concentrations. This multiphase growth is reflected in the patchy distribution of F in the Negev constituents and might explain the inverse correlation between mean CO₂/F and F/P₂O₅ ratios of the analysed phosphorites in the two facies. It also suggests that CFA (or an amorphous precursor) initially formed with some OH groups in the apatite structure, which were subsequently substituted by F ions in recycled francolite through re‐equilibration with porefluids of higher F concentrations.     

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.     

Uranium (U) concentration and its genetic significance in the phosphorites of the Paleoproterozoic Bijawar Group of the Lalitpur district,Uttar Pradesh,India

The paper presents the uranium (U) concentration and distribution pattern in the Paleoproterozoic phosphorites of Lalitpur district of Uttar Pradesh. The study of thin sections, SEM and XRD reveal that apatite is the essential phosphate mineral while quartz and feldspars are the dominant gangue in the phosphorites of the investigated area. The collophane is observed to be mostly oolitic in form and microspherulitic in texture. The major element geochemistry indicated that the phosphorite samples are rich in P₂O₅, CaO, SiO₂ and Fe₂O₃ whereas depletion of MgO, MnO, K₂O and Al₂O₃ was observed. The CaO/P₂O₅ ratio ranges from 1.13 to 1.46 which is slightly lower than that of cations and anions substituted francolite (1.621) and close to that of carbonate-fluorapatite (1.318). The trace element geochemistry indicates that the phosphorites of Lalitpur have the significant range of U concentration (1.67 to 129.67 μg/g) which is more than that of Th (0.69 to 0.09 μg/g) among the analysed trace elements in the phosphorite samples of the area. The positive correlation of U with P₂O₅, CaO and U/P₂O₅ indicates a close association of U with phosphate minerals like collophane (apatite), whereas negative correlation of U with SiO₂ and Fe₂O₃ may be due to mutual replacement. The antipathetic relationship of U with Ni may be an indication of high oxidizing conditions, whereas sympathetic relationship of U with K₂O points towards higher alkaline conditions of the basin of deposition during phosphatization. The variable concentration of U and its relationship with significant major and trace elements in most of the phosphorite samples lead one to believe that the deposition of these phosphorites might have taken place in highly alkaline medium during fairly oxidizing to weakly reducing environmental conditions of geosynclinal basin.     

Origin of Cretaceous phosphorites from the onshore of Tamil Nadu,India

Cretaceous phosphorites from the onshore of Tamil Nadu have been investigated for their origin and compared with those in the offshore. Cretaceous phosphorites occur as light brown to yellowish brown or white nodules in Karai Shale of the Uttatur Group in the onshore Cauvery basin. Nodules exhibit phosphatic nucleus encrusted by a chalky shell of carbonate. The nucleus of the nodules consists of light and dark coloured laminae, phosphate peloids/coated grains and detrital particles interspersed between the laminae. Scanning electron microscope (SEM) studies reveal trapping and binding activity of microbial filaments. A mat structure with linearly arranged microbial filaments and hollow, cell-based coccoid cyanobacterial mat are present. Nodules contain abundant carbonate fluorapatite, followed by minor calcite, quartz and feldspar. The P₂O₅ content of the phosphorites ranges from 18 to 26%. The CaO/P₂O₅, Sr and F contents are higher than that of pure carbonate fluorapatite. Concentrations of Si, Al, K, Fe, and Ti are low. We suggest that the nuclei of the nodules represent phosphate clasts related to phosphate stromatolites formed at intertidal conditions. At high energy levels the microbial mats were disintegrated into phosphate clasts, coated with carbonate and then reworked into Karai Shale. On the other hand, Quaternary phosphorites occur as irregular to rounded, grey coloured phosphate clasts at water depths between 180 and 320m on the continental shelf of Tamil Nadu. They exhibit grain-supported texture. Despite Quaternary in age, they also resemble phosphate stromatolites of intertidal origin and reworked as phosphate clasts onto the shelf margin depressions. Benthic microbial mats probably supplied high phosphorus to the sediments. Availability of excess phosphorus seems to be a pre-requisite for the formation of phosphate stromatolites.     

Geochemistry of Phosphorus and Origin of Phosphorites: Communication 1. Role of Terrigenous Material in the Hypergene Phosphorus Geochemistry

Different hypotheses of phosphorite formation are discussed. The biogenic origin of phosphorites is most plausible. The important role of terrigenous material in P₂O₅ migration and concentration in the hypergenesis zone is emphasized. The mineralogical zoning of phosphate accumulations is described and the probable diagenetic alteration of accessory apatite in present-day seas and lakes is affirmed.     

Uranium in supergene phosphorites

The distribution of uranium was studied in supergene phosphorites from the zones of the weathering of sedimentary and endogenous rocks, as well as in nonmarine coprolitic phosphorites and, to a lesser extent, phosphorites from ocean islands. These phosphorites show a diversity of the composition of their carbonate-apatite and structural characteristics. The uranium content ranges mostly from 5 to 100 ppm, with minimum and maximum values of 0.5 and 790 ppm. There is no correlation between the uranium content of a phosphorite and the type of rock with which it is connected. Lacustrine coprolitic phosphorites show elevated uranium contents (about 200 ppm). The maximum uranium content was detected in finely laminated phosphorite encrustations. The correlation analysis of the whole data set (63 samples) showed that uranium content is not correlated with any other component of phosphorites at a confidence level of 0.95. In contrast, there is a correlation between U and P₂O₅, CaO, and F for the combined set of samples from southern Siberian deposits. The significant correlation of U with Na₂O and CO₂ is variable both for southern Siberia on the whole and for particular deposits from this region.     

Geochemical Characteristics of Apatite in Heavy REE‐rich Deep‐Sea Mud from Minami‐Torishima Area,Southeastern Japan

We have conducted geochemical and mineralogical investigations of the rare earth and yttrium (REY)‐rich mud from the Minami‐Torishima area in the Pacific in order to clarify the concentration of REY and their host‐phase in the mud. X‐ray diffraction analysis shows that the mud is mainly composed of phillipsite, fluorapatite, quartz, albite, illite and montmorillonite. Whole‐rock CaO, P₂O₅ and total REY contents of the mud are positively correlated. Relative abundance of apatite is also positively correlated to P₂O₅ and total REY contents. These correlations suggest that apatite is the main host of the P₂O₅ and REY in the mud. We make in situ compositional analyses of constituent minerals in the REY mud. The results show that the apatite is abundant in REY (9300–32,000 ppm) and is characterized by a negative Ce anomaly and enrichment in heavy rare‐earth elements. This abundance and composition of REY of the mud is similar those of fish debris apatites. In contrast, phillipsite is less abundant in REY (60–170 ppm). Therefore we conclude that the main REY host phase of the mud is apatite.     

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。     

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.     

Quaternary phosphorites off the southeast coast of India

Detailed petrological, mineralogical, geochemical and radiogenic (U, Sr, Nd) and stable isotope (C, O, S) studies have been carried out on the Quaternary phosphorites of the continental margin off Chennai, southeast coast of India. These phosphorites are formed as a result of trapping and binding of sediments by microbial mats and are similar to phosphate stratiform stromatolites. Detrital and biogenic constituents enclosed in the phosphorites controlled the major and minor element composition. Except for Sr and U, the concentrations of most of the trace metals are lower than those in average shale and phosphorite. Middle rare earth element (MREE)-enriched patterns are the characteristic feature. The U–Th dating method indicates that the ages of the phosphorites are beyond 300,000 years. ⁸⁷Sr/⁸⁶Sr ratios of the phosphorites are higher than that of present-day seawater and εNd values are more negative than those of seawater of the Atlantic Ocean. Carbon isotope ratios are within the range expected for the oxic/suboxic zone but sulfur isotope ratios indicate suboxic conditions during phosphorite formation. These results imply that the benthic microbial mats thrived on the shallow shelf during the Quaternary low sea level conditions. Periodic or episodic sedimentation onto the mats led to their death. The bacteria associated with decaying microbial mats utilised phosphorus supplied by continental sources and rapidly precipitated phosphate. The availability of a high percentage of phosphorus in seawater seems to be an important controlling factor for the formation of phosphate stromatolites. The composition of these phosphorites differs from the modern phosphorites in upwelling regions, but are similar to Cambrian apatite stromatolites. These phosphorites provide evidence that the replicates of ancient phosphate stromatolites do exist in the Quaternary.     

Proposed upgrading techniques for East Sibaiya phosphorites,Aswan area,southern Egypt

The Late Cretaceous (Campanian-Maastrichian), low-grade phosphorite sequence of East Sibaiya, Aswan area, which is known as the Duwi (phosphate) or Sibaiya Formation, is usually intercalated with marl, oyster limestone, and chert beds. These strata, which crop out in a generally east–west trending belt spanning the middle latitudes of Egypt, are phosphorite-rich sediments and of great economic importance. Representative samples were collected from the investigated area at several localities (e.g., Umm Tundubah-2 and Wadi El-Batur) and 200 kg of phosphate rocks was used for upgrading processes of low-grade phosphorites of the East Sibaiya area. The upgrading processes included two techniques: the first technique (gravity separation) comprises crushing, sieving, gravity separation by a shaking table, and magnetic separation. This technique raised the P₂O₅ in the head sample from 24.73 to 31.91% as a phosphate concentrate. The second technique (flotation technique) depends on certain flotation parameters such as pH, grain size, and phosphate collector dose (i.e., oleic acid). The flotation technique increased the P₂O₅% from 24.73 to 31.16% as a final product of the phosphate concentrate. These data were confirmed by X-ray fluorescence analyses of major elements.     

Phosphorites of the Chiatura manganese deposit and specific features of their formation

The paper presents results of the detailed study of phosphorites from manganiferous beds of the Chiatura deposit. The relatively high-grade (P₂O₅ 20–28%) phosphorites are represented by various rocks ranging from the variety dominated by massive phosphates with a rare aleuritic admixture of quartz and feldspar grains to rocks mainly composed of terrigenous material with phosphates in the matrix. Phosphates make up the matrix of various organic remains: differently preserved diatom algae and microbial species. Some relatively large organic remains (in particular, sponge spicules) are typically composed of iron minerals (with manganese admixture) rather than phosphates. Manganese ores comprise phosphorite fragments composed of phosphatized cyanobacterial mat. Phosphorites of the Chiatura deposit were likely formed in a shallow-water zone away from the continental land.     

Geochemical and statistical characterization of the phosphate facies of the Farim‐Saliquinhé phosphate mineralization (Guinea‐Bissau)

The Eocene Farim‐Saliquinhé phosphate mineralization (FSPM) is a buried sedimentary deposit located in the northern part of Guinea‐Bissau, discovered and spatially constrained during the 1980s by the French Geological Survey (BRGM). In the present work some of the data collected at that time are reworked in the framework of the development of a 3D geological and geochemical model of this mineralization. We show the usefulness of two classical multivariate statistical methods – principal component analysis (PCA) and cluster analysis (CA) – applied to eight geochemical variables (P₂O₅, SiO₂, Al₂O₃, Fe₂O₃, CaO, MgO, F and CO₂) measured in 247 samples from phosphate facies, for differentiation of samples taken from the different phosphate facies recognized in the FSPM, namely the main ore FPA (30 to 35% high grade phosphate), the calcareous low grade phosphate FPB (10 to 20% P₂O₅) (both Lutetian), and a mineralized Upper Eocene to Lower Oligocene cover (mainly including the FPO level and a silico‐aluminous phosphate bed), overlying the FPA, which can also be considered a third set of phosphate facies associated with the FSPM.     

Uranium in Phosphorites

The uranium concentration in phosphorites on continents and modern seafloor varies from 0.nto n· 10²ppm (average 75 ppm). The average uranium concentration is 4–48 ppm in Precambrian and Cambrian deposits, 20–90 ppm in Paleozoic and Jurassic deposits, 40–130 ppm in Late Cretaceous–Paleogene deposits, 30–130 ppm in Neogene deposits, and 30–110 ppm in Quaternary (including Holocene) deposits. On the whole, the variation range is almost similar for phosphorites of different ages. The U/P₂O₅ratio in phosphorites ranges from less than unity to 24 · 10^–4(average 3.2 · 10^–4). Major phosphorite deposits of the world with ore reserves of approximately 250 Gt (or 58 Gt P₂O₅) contain up to 19 Mt of uranium. Uranium is present in phosphorites in the tetra- and hexavalent, i.e., U(IV) and U(VI) forms, and their ratio is highly variable. At the early diagenetic stage of the formation of marine phosphorites in a reductive environment, U(VI) diffuses from the near-bottom water into sediments. It is consequently reduced and precipitated as submicroscopic segregations of uranium minerals (mainly uraninite) that are probably absorbed by phosphatic material. During the subsequent reaction between phosphorites and aerated water and the weathering in a subaerial environment, uranium is partly oxidized and lost. The uranium depletion also occurs during catagenesis owing to a more complete crystallization of calcium phosphate and replacement of nonphosphatic components.     

Trace elements in supergene phosphorites

Supergene phosphorites were analyzed for Sr, Ba, Zn, Cd, Sc, Cr, Ag, and V, i.e., elements incorporated in carbonate-apatite by isomorphic substitution. The phosphorites were subdivided into four groups: (1) phosphorites related to the weathering of sedimentary rocks, (2) phosphorites related to the weathering of endogenous rocks, (3) lacustrine coprolite phosphorites, and (4) phosphorites of ocean islands. In all the phosphorites groups, Sr, Zn, and Ba were the most abundant of the trace elements, whereas Cd, Ag, and Sc showed the lowest concentrations. Variations in trace element contents between supergene phosphorites of different genetic groups or within a single group can be explained by the different compositions of weathered rocks and geochemical environments of supergene phosphorite formation. At the same time, the contents of some trace elements are correlated with the structural type of phosphorite. In particular, phosphorite crusts or only their outer parts show elevated contents of chalcophile elements (Cd, Zn, and Ag), whereas massive phosphorites and inner parts of crusts are often enriched in such lithophile elements as Sc, V, and Cr. It was found that Cd, Zn, Ag, Sr, and Ba are positively correlated with CO₂ but show negligible correlations with other constituents of carbonate-apatite.     

Fluorine in lunar samples: implications concerning lunar fluorapatite

The F contents of a number of Apollo 14 and 15 samples range from less than a ppm for anorthosite rock fragments to ~165 ppm for some soils and breccias. Apollo 15 soils tend to have lower F contents (50–70 ppm) than soils from other sites. In most cases samples were run simultaneously with W-1 in which F was determined to be 216 (±11) ppm.The $\text{F}\text{P}{}_2\text{O}{}_5$ ratio is 0·032 ± 0·005 in soils and rocks. A correlation exists in soils between F, P₂O₅, and that fraction of the Cl which is insoluble in hot water. The $\text{F}\text{Cl}{}_{\mathrm{r}}$ ratio in soils and rocks, though different, requires that the phosphate phase involved be fluorapatite; this is consistent with mineralogical observations. F, like Cl, is correlated with KREEP elements at all sites for which data are available.     

Lower Eocene phosphorites of the western desert,Iraq

Marine sedimentary phosphorites of Eocene age (Upper Ypresian) are exposed in the extreme west of Iraq within the Dammam Formation. They are associated with limestone and chert, and their deposition seems to have taken place in a shallow marine environment within a structurally controlled basin open to the sea from the northern and western sides only.The studied phosphorites are granular in texture, coarse-grained and cemented by calcite which is occasionally silicified. Bone fragments are present in small amounts. Carbonate-fluorapatite is the only phosphate mineral detected in these phosphorites, with relatively high amounts of the components SO₄^?2, CO₃^?2, F^?1, H₃O¹ and Na¹ substituting in the crystal structure.The Lower Eocene phosphorites of Iraq are part of the Tethyan phosphorite province, and are comparable in many aspects with those of Paleocene and Upper Cretaceous age in the Western Desert of the country.     

Problems of Iron and Phosphorus Geochemistry in the Precambrian

The localization of economic sedimentary iron ore and phosphorite resources is discussed in comparative aspects. It is shown that the major economic resources of iron ore are hosted in Precambrian rocks, whereas the phosphorites are related to Upper Phanerozoic. High-temperature hydrothermal solutions served as an important source of iron for jaspilite ores. The low P₂O₅content therein indicates that the phosphorus deposition was only weakly related to the hydrothermal activity. Thus, the hydrothermal origin of phosphorite is denied from the geochemical standpoint.     

磷块岩形成过程中的生物作用

 对我国震旦纪、寒武纪磷块岩矿床的研究表明,参与成磷作用的生物主要是菌、藻类微生物。生物作用的标志表现为:P₂O₅主要富集在叠层石磷块岩中,富集在叠层石的柱体上,富集在柱体内部的富藻纹层中;而与磷块岩共生的白云石和黄铁矿的δ¹³C值和δ³⁴S值相对均较低,则是生物参与成磷作用的同位素标志特点。生物的成磷作用贯穿成磷过程的始终,但它随作用的相带、环境和阶段不同,生物的种属和作用方式也不同,因而矿石和矿床的质量也随之而异。     

Precambrian phosphorites in the Bijawar rocks of Hirapur-Bassia areas,sagar district,madhya pradesh,India

The Precambrian phosphorites of Bijawar Group of rocks show characteristics of a epicontinental sea with restricted and very shallow marine environment of formation along some shoals, which existed during the iron-rich Precambrian times. These phosphorite deposits located in the Hirapur-Bassia areas show extensive leaching of carbonate and phosphate minerals during episodes of weathering. X-ray diffraction studies indicated that carbonate-flourapatite is the major apatitic phase in these phosphorites while crandallite developed on the surface outcrops. There is a general tendency for the depletion of CO₂ in these apatites leading to formation of flourapatite. This CO₂ is an indicator of hidden weathering in the rocks. Major and trace element determinations of phosphorite have been used to indicate various correlation factors responsible for the concentration of elements in these Precambrian leached phosphorites.The paper is a contribution to the aims and objectives of IGCP Project 156The paper is dedicated to Prof. Dr. R. C. Misra, who as a teacher and guide had been a source of inspiration to the senior author for the last two decades