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.     

Effect of the depositional environment on the compositional variations among the phosphorite deposits in Egypt

Late Cretaceous economic phosphorites from the Red Sea, Nile Valley, and Abu Tartur areas, Egypt, show distinct variations in the lithology of associated sediments, mineralogy of nonphosphatic constituents, and distributions of major and trace elements. In the Red Sea area, the phosphorite beds are intercalated with laminated black shales, and the nonphosphatic constituents are detrital quartz and calcite, ankerite, and pyrite cements. In the Nile Valley, the phosphorite beds are intercalated with chert, marl, and sandstone and the nonphosphatic constituents are detrital quartz and calcite and chalcedony cements. In the Abu Tartur Plateau, the phosphorite beds are intercalated with laminated black shales, and the nonphosphatic constituents are detrital quartz and ankerite and pyrite cements. The phosphorites studied also show distinct variations in major- and trace-element concentrations. The Abu Tartur phosphorites have higher contents of TiO₂, Al₂O₃, Fe₂O₃, K₂O, Co, Nb, Pb, Sr, Th, Y, and Zr and lower SiO₂, Ba, and U contents as compared to those in the Red Sea and Nile Valley areas. The positive correlations between Al₂O₃ and TiO₂, K₂O, Nb, Y, and Zr suggest the detrital origin of these constituents.Similarity in the phosphatic constituents, which were derived from outside the depositional sites, and variations in the lithology of associated sediments and the mineralogy and geochemistry of the nonphosphatic constituents, which reflect the conditions at the depositional sites, suggest that the variations in the depositional environment of the phosphorites are the potential controlling factor of the compositional variations among these phosphorites. The abundance of black shales in the Red Sea and Abu Tartur areas, as well as the occurrence of ankerite and pyrite as cementing materials for the phosphatic constituents, might reflect reducing conditions in these areas, while the abundance of siliciclastic sediments and calcite and chalcedony cements suggests oxidizing conditions in the Nile Valley. The reducing conditions in the Red Sea and Abu Tartur areas were probably developed within the pre-existing depressions in a shelf environment. These depressions might have formed as a result of a change in the movements of the North Atlantic, Eurasian, and African Plates during the late Santonian, which led to transgressive inversion of rifts along northern Egypt and consequent folding in the continental interior. The higher contents of detrital components in the Abu Tartur phosphorites compared to the Red Sea and Nile Valley areas suggest more detrital inputs during the deposition of the phosphorites in Abu Tartur. The products of the diagenesis and weathering of these deposits also reflect the variations in the depositional conditions.     

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.     

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.     

Mineralogy,geochemistry and the origin of high-phosphorus oolitic iron ores of Aswan,Egypt

The Coniacian-Santonian high-phosphorus oolitic iron ore at Aswan area is one of the major iron ore deposits in Egypt. However, there are no reports on its geochemistry, which includes trace and rare earth elements evaluation. Texture, mineralogy and origin of phosphorus that represents the main impurity in these ore deposits have not been discussed in previous studies. In this investigation, iron ores from three localities were subjected to petrographic, mineralogical and geochemical analyses. The Aswan oolitic iron ores consist of uniform size ooids with snowball-like texture and tangentially arranged laminae of hematite and chamosite. The ores also possess detrital quartz, apatite and fine-grained ferruginous chamosite groundmass. In addition to Fe₂O₃, the studied iron ores show relatively high contents of SiO₂ and Al₂O₃ due to the abundance of quartz and chamosite. P₂O₅ ranges from 0.3 to 3.4 wt.% showing strong positive correlation with CaO and suggesting the occurrence of P mainly as apatite. X-ray diffraction analysis confirmed the occurrence of this apatite as hydroxyapatite. Under the optical microscope and scanning electron microscope, hydroxyapatite occurred as massive and structureless grains of undefined outlines and variable size (5–150 μm) inside the ooids and/or in the ferruginous groundmass. Among trace elements, V, Ba, Sr, Co, Zr, Y, Ni, Zn, and Cu occurred in relatively high concentrations (62–240 ppm) in comparison to other trace elements. Most of these trace elements exhibit positive correlations with SiO₂, Al₂O₃, and TiO₂ suggesting their occurrence in the detrital fraction which includes the clay minerals. ΣREE ranges between 129.5 and 617 ppm with strong positive correlations with P₂O₅ indicating the occurrence of REE in the apatite. Chondrite-normalized REE patterns showed LREE enrichment over HREE ((La/Yb)_N = 2.3–5.4) and negative Eu anomalies (Eu/Eu* = 0.75–0.89). The oolitic texture of the studied ores forms as direct precipitation of iron-rich minerals from sea water in open space near the sediment-water interface by accretion of FeO, SiO_2, and Al₂O₃ around suspended solid particles such as quartz and parts of broken ooliths. The fairly uniform size of the ooids reflects sorting due to the current action. The geochemistry of major and trace elements in the ores reflects their hydrogenous origin. The oolitic iron ores of the Timsha Formation represent a transgressive phase of the Tethys into southern Egypt during the Coniacian-Santonian between the non-marine Turonian Abu Agag and Santonian-Campanian Um Barmil formations. The abundance of detrital quartz, positive correlations between trace elements and TiO₂ and Al₂O₃, and the abundance mudstone intervals within the iron ores supports the detrital source of Fe. This prediction is due to the weathering of adjacent land masses from Cambrian to late Cretaceous. The texture of the apatite and the REE patterns, which occurs entirely in the apatite, exhibits a pattern similar to those in the granite, thus suggesting a detrital origin of the hydroxyapatite that was probably derived from the Precambrian igneous rocks. Determining the mode of occurrence and grain size of hydroxyapatite assists in the maximum utilization of both physical and biological separation of apatite from the Aswan iron ores, and hence encourages the use of these ores as raw materials in the iron making industry.     

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。     

滇池地区沉积磷块岩中胶磷矿矿物学特征及其研究意义

本文从物理性质、化学成分及其成因结构等方面,对云南滇池地区胶磷矿进行了矿物学特征研究。提出该区胶磷矿主要以三种形式赋存在磷块岩中。对不同矿石类型中胶磷矿做扫描电镜研究,得知胶磷矿主要由超微晶低碳氟磷灰石集合体、磷酸盐显微莓群以及纤维放射状磷灰石等构成。经化学分析、红外、晶胞参数测定,不同胶磷矿有一定差异,特别是碳和磷,经矿物学对比发现,反映随变质作用的加深,胶磷矿有向晶质氟磷灰石演化的趋势,脱碳作用表现明显。本区胶磷矿稀土元素含量不高,钇族较富,铈族较贫。球粒陨石标准化后为铈亏损型模式。     

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.     

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.     

Mineralogical and geochemical investigation of clay-rich mine tailings from a closed phosphate mine, Bartow Florida, USA

Clay-rich mine tailings from phosphate mine operations in Florida are a major environmental and economic problem. Options for reclamation and restoration for these tailings are very limited and are fundamentally restricted by poor physical properties such as low mechanical strength, low hydraulic conductivity, and heavy metal content. The major control on these bulk physical properties is the mineralogy of the materials. Eight continuous push borings were obtained to investigate stratigraphy, mineralogy, aspects of geochemistry, and bulk properties of a deposit of clay-rich mine tailings from a phosphate mine near Bartow, Florida that ceased operations in the early 1970s. Stratigraphy is dominated by laminated clay-rich sediment with minor units of silt and sand. An intact kaolinite liner occurs near the impoundment walls and the impoundment floor has approximately 4 m of relief. Moisture content varies from 4.35 to 57.40 wt% and organic content varies from 0.41 to 9.53 wt%. Bulk XRF investigation indicates that the P₂O₅ concentrations vary from approximately 4 to 21 wt%. A very strong correlation (r ² = 0.92) between CaO and P₂O₅ indicates that apatite is a major control on the phosphate. The strong correlation (r ² = 0.77) of Al₂O₃ and TiO₂ suggests that the source materials for this deposit are comparatively uniform. A number of heavy metal elements and trace elements occur. Cr, V, Ni, Cu are interpreted to be in phosphate minerals, largely apatite. Sr and Pb are interpreted to be in both phyllosilicates and phosphate minerals. Two populations of apatite were observed in the clay-sized fraction, one that was Fe and Si- bearing and another that was only Si-bearing. Fe-bearing apatite had Fe₂O₃ contents that varied from 0.38 to 5.32 wt% and SiO₂ contents that varied from 0.90 to 3.32 wt%. The other apatite population had a wider range of SiO₂ contents that varied from 0.77 to 8.80 wt%. TEM imaging shows that apatite grains are dominantly single crystals with lesser amounts of aggregates. Wavellite commonly occurs as individual or clusters of lath-like crystals and the chemical composition differs from the pure aluminium phosphate end member with average concentrations of components being that of CaO (1.57 wt%), Fe₂O₃ (1.98 wt%), SiO₂ (5.94 wt%). In the clay-sized phosphate minerals investigated no fluorine was found above detection limit (approximately 0.15 wt%), nor was any uranium, radium, heavy metal, or REE element detected. The phyllosilicate mineralogy of the deposit is dominated by smectite (montmorillonite with lesser amounts of nontronite), palygorskite, illite and kaolinite. No systematic variation in the relative proportions of phyllosilicates was observed in the clay deposit. Energy dispersive spectroscopy EDS analysis indicates that chemical compositions of phyllosilicates are somewhat typical but overall are enriched with respect to Fe compared to theoretical end members. The relative enrichment of Fe is interpreted to be a primary sedimentary feature. Ca content in smectite minerals is high and may inhibit stabilization using lime or similar methods. The high percentages of montmorillonite and palygorskite explain the high bulk water contents observed. This investigation provides fundamentally new details regarding clay tailing deposits from closed phosphate mines in central Florida which can be used in restoration and reclamation efforts.     

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.     

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.     

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.     

云南省镇雄县羊场磷矿地球化学特征及其沉积环境分析

羊场磷矿是近年来在云南评价确认的沉积大型磷矿床,磷矿体赋存于下寒武统梅树村组碳酸盐岩-泥质碎屑岩沉积中部的一套含磷岩系中,呈层状、似层状展布于羊场背斜两翼,其产状与地层产状基本一致,含矿岩性为含磷白云岩、磷质岩、磷块岩、硅质岩建造。通过分析该矿床矿体特征和梅树村组磷块岩的主微量元素组成,研究了羊场磷矿的地球化学特征及其沉积环境。结果表明,羊场磷矿磷块岩具有富钙（w（CaO）=42.07%~45.01%）、磷（w（P₂O₅）=27.66%~39.25%）和贫硅（w（SiO₂）=8.27%~15.40%）的特征;w（P₂O₅）与w（CaO）呈较好的正相关关系,与w（MgO）呈负相关关系,与w（Al₂O₃）呈较明显的负相关关系。矿石的w（Th）/w（U）值小于1、Pb （亲硫元素）和Sr富集（Pb平均富集系数16.66,Sr平均富集系数1.17）特征表明,羊场磷矿可能是热水沉积成矿与生物成矿双重作用的结果;微量元素特征值反映,羊场磷矿形成于深海到浅海的变化环境,为海相沉积型磷块岩,沉积时水体呈还原环境。     

Iodine in karst-type phosphorites from the Lahn region,Germany

The concentration of iodine in 31 Tertiary continental phosphorites from the Lahn region in Germany ranges from about 0.01% to 0.18%, the mean value of 0.044% being quite compatible with that of typical commercial-grade iodine deposits. Microscopic and X-ray diffractometric studies manifested three main mineral phases in these phosphorites viz. francolite, clay minerals (kaolinite, illite), and ferric oxides (goethite, hematite). These mineral phases were investigated for iodine distribution, mode of its fixation and possible source. Sample heating at 600°C evinced no appreciable organic matter in the sample and further showed that the iodine was non-volatile in character. Regression analysis revealed a good correlation between I and Al (Ti), practically no correlation with Fe and negative correlation with P₂O₅. It was thus deduced that the iodine content is inorganic in nature and bound principally and probably internally to Al-bearing minerals. An iodine content of about 150 ppm is believed to be associated with the apatite phase of the phosphorite.Devonian volcanic rocks are assumed to be the ultimate source of both phosphorus and iodine. Those elements were released during a Tertiary weathering period, their accumulation being controlled by chemical environment and karst topography of a Devonian reef limestone.     

Dispersion of niobium and phosphorus in soil overlying the Qaqarssuk Carbonatite Complex, Southern West Greenland

Rocks and soils overlying the Qaqarssuk Carbonatite Complex, southern West Greenland, were analyzed for major and trace elements by various analytical methods. The carbonatitic rocks contain up to 5% P₂O₅ and up to 0.2% Nb. The soils are relatively depleted in Ca due probably to dissolution of calcite by CO₂-rich waters. Apatite is not affected by this mechanism so that P₂O₅ tends to be enriched in the soils. A CaO/MgO ratio of less than about 1.5 is indicative of apatite accumulation in the soils. The dominant carbonate mineral in soils is dolomite and secondary apatite was not observed. Soil grains are angular and not seriously affected by mechanical transport. The investigations show that soil sampling for geochemical exploration in the arctic environment is suitable for mapping and prospecting for carbonatites.     

The incorporation of uranium into diagenetic phosphorite

The behavior of U during the diagenetic formation of marine phosphorite has been modelled. The model examines a dissolution-reprecipitation replacement of skeletal hydroxyapatite, calcium carbonate and earlier generated francolite by francolite. The amount of organic matter consumed relative to the mass of francolite formed, the replacement reaction progress, and the concentration of U in the replaced phases are the important parameters which dictate the concentration of U in the phosphate rock.A partition coefficient between apatite and interstitial solution was calculated, and is $\text{λ}{}_{\mathrm{U}}{}^{\mathrm{F}}\text{= 0.57}$.Natural phosphorites have been examined and are discussed in the light of the proposed model. The U mass-balance in a Recent phosphorite is in good accord with theoretical predictions. Differences in U concentrations between sea-floor phosphorites are explained either by the (original) variation in the organic matter distribution in the corresponding sediments and/or by mineralogical differences (CaCO₃vs. hydroxyapatite) therein.Senonian phosphate rocks which were formed via the francolite → francolite transformation, demonstrate that during that process the organic matter content in the sediment was approximately 50%.The model supports the idea that phosphorite rock formation is a multistage process.     

昆明晋宁王家湾磷矿矿石组份再研究

胶磷矿的矿物组成,主要是微碳—低碳磷灰石,及细晶磷灰石。而胶磷矿细微颗粒,经电镜观察鉴定,主要由磷酸盐化有机碎屑及藻席碎屑组成,早寒武世磷块岩的形成是生物学、沉积学、古地理—古构造等综合因素沉积作用的产物。     

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     

Geochemistry of major and trace elements and Pb–Sr isotopes of a weathering profile developed on the Lower Cambrian black shales in central Hunan,China

This paper reports a geochemical study on the major and trace elements and Pb–Sr isotopes of a weathering profile developed in the Lower Cambrian black shales in central Hunan (China). Six weathering horizons were identified and sampled vertically throughout the profile. The chemical composition of the profile consists of variable concentrations of the major elements Fe₂O₃, FeO, MnO, MgO, CaO, Na₂O, and P₂O₅ and of less variable concentrations of SiO₂, TiO₂, Al₂O₃, and K₂O. The chemical change caused by weathering is estimated by mass-balance calculations, and the results show that the element mobility is characterised by substantial loss of SiO₂, FeO, CaO, K₂O, Na₂O, LOI, Cr, V, Ba, Cs, Rb, Sr, U, and Th, and moderate loss of Al₂O₃, MgO, Fe₂O₃, Ni, Cu, Pb, Tl, Sn, Sc, Ge and REE (Y). The high field strength elements TiO₂, Sn, Sc, U, Ga, Ge, Zr, Hf, Nb, and Ta were immobile during weathering. The chemical changes and the Pb–Sr isotopic data suggest that four types of chemical reactions occurred: the oxidation of sulphide minerals (e.g., pyrite) and organic carbon (OS), the dissolution of less resistant clinochlore-Ia, calcite, and P-bearing minerals (DL), the dissolution of detrital albite and microcline (DA), and the transformation of clay (TC) minerals (e.g., muscovite and illite–smectite). These chemical reactions then led to two stages of geochemical processes, an early stage of chemical differentiation and a later stage of chemical homogenisation. The chemical differentiation dominated by the OS, DL, and DA reactions, led to the leaching of mobile elements (e.g., MgO, Na₂O, K₂O, P₂O₅, Sr, and REE) and the redistribution of some less mobile elements (e.g., SiO₂ and Al₂O₃). In contrast, the chemical homogenisation, which was caused by TC reactions, led to the leaching of both mobile and less mobile elements from the system and ultimately transformed the weathered black shales into soil. Soils derived from black shales in South China might result from the above two geochemical processes.