An occurrence of cadmiferous phosphorite soil concretions in Jamaica

Bauxite exploration drilling revealed the presence of phosphate minerals through the chemical and XRD analysis of recovered drill hole samples at Spitzbergen, in Manchester Parish, Jamaica. A subsequent pit led to the discovery of phosphorite concretions composed of hard competent masses of finely crystalline fluorapatite, with some minor crandallite. The phosphorite contains anomalously high levels of Zn (>5000 mg kg⁻¹), Cd (>1.1%), Ag (>20 mg kg⁻¹), Be (>80 mg kg⁻¹) and, to a lesser extent, U. Textural and geochemical evidence indicates that the phosphorite concretions were most likely formed by the replacement of limestone by secondary deposition proximal to fossil guano deposits, postulated to be Late Miocene or Pliocene sea-bird colonies. Mechanical dispersion of the phosphorite concretions through karst weathering processes has led to their wider spatial distribution than the original guano deposits. Subsequent weathering of the concretions and the admixture of their decomposition products into the bauxitic and Terra Rossa soils is postulated to be the cause of the widespread anomalous levels of Zn, Cd and Be in these soils in central Jamaica, and the elevated levels of P in the bauxite.     

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.     

Geochemistry of Cadmium in Mesozoic Phosphorites of the East European Platform

Cadmium is the most toxic admixture in mineral fertilizers. The Cd concentration in Mesozoic phosphorites, which are widespread in the East European Platform, has not been investigated. The present study was stimulated by the scanty and contradictory nature of the published data on this issue. We determined Cd concentration in 21 phosphorite samples from major deposits and checked the reliability of obtained results by external replicate analyses. It has been established that the Cd concentration in phosphorites varies from 5 ppm in the Late Jurassic–Early Cretaceous basin to 2 ppm in the Late Cretaceous basin. Cadmium does not enter the structure of phosphate and sulfide minerals. The Cd concentration is independent of the phosphorus abundance. However, all studied samples show a positive correlation of Cd with organic matter mainly contained in phosphates, supporting the biophilic nature of Cd. Mesozoic phosphorites of the East European Platform accumulated in epicontinental basins. They are significantly depleted in Cd relative to Mesozoic–Cenozoic phosphorites in pericontinental basins of the southern margin of the Tethys Ocean. The Cd concentration is more stable in Mesozoic phosphorites than in Mesozoic–Cenozoic deposits.     

The pollution of marine sediments by trace elements in the coastal region of Togo caused by dumping of cadmium-rich phosphorite tailing into the sea

 The marine coastal sediments from Togo have been analysed for the trace elements Cd, Cr, Cu, Ni, Pb, Sr, V, Zn and Zr to ascertain the geo-ecological impact of dumping of phosphorite tailings into the sea. Trace element concentrations ranged from 2–44 ppm for Cd, 22–184 ppm for Cu, 19–281 ppm for Ni, 22–176 ppm for Pb, 179–643 ppm for Sr, 38–329 ppm for V, 60–632 ppm for Zn and 18–8928 ppm for Zr. Regional distribution of trace elements in the marine environment indicates that the concentrations of Cr, Cu, Ni, Pb, V, Sr and Zn increase seawards and along the coastal line outwards of the tailing outfall, whereas Cd and Zr showed reversed spatial patterns. Sorting and transport of phosphorite particles by coastal currents are the main factors controlling the distribution of particle-bound trace metals in the coastal environment. The Cd, Sr and Zn concentrations decrease with decreasing grain size in marine coastal sediments, whereas Cr, Cu, Ni and Zn concentrations increase with decreasing grain size. Percolation and shaking experiments were carried out in laboratory using raw phosphate material and artificial sea water. Enhanced mobilization of Cd from phosphorites by contact with the sea water was observed. Received: 11 May 1998 · Accepted: 20 October 1998     

沉积磷块岩结构类型、成因及成矿阶段

磷块岩的岩石类型和成矿阶段划分是磷块岩研究的一项基础性工作,早在50年代后期,叶连俊等人就对磷块岩及其分类进行过研究[1],随着沉积学的发展,尤其是近年来碳酸盐岩研究的进展,磷块岩岩石学研究也有了一些新的突破。磷块岩分类从矿体形态(层状、透镜状、结核状)、大地构造(地台型、地槽型)等分类走向了结构成因分类。在这方面,工作较多,较系统的有美国的S.R.Riggs和法国的M.S1ansky[9][10]。我国的孙枢、陈其英、赵东旭[2][3]及孟祥化[4]、周茂基[5]、东野[6]等人也先后对磷块岩的结构成因类型进行过研究。这些研究给磷块岩的分类奠定了一个很好的基础。     

Comparative geochemistry of shell phosphorites and dictyonema shales of the Baltic

Major and trace element composition of the Ordovician Obolus phosphorites and associated Dictyonema shales were determined by ICP-MS and chemical and microchemical elemental analyses. Relative to the phosphorites, the Dictyonema shales are substantially enriched in a variety of trace elements, except for As, Be, Co, Y, REE, Sr, and Pb. The Obolus phosphorites show enrichment of As, Bi, Hg, Mo, La, Y, Pb, and Sr and depletion of Ag, Ba, Be, Cd, Cr, Cu, Hf, Ni, Sc, Sn, U, V, Zn, and Zr relative to the world average phosphorite composition. The average trace element composition of the Dictyonema shales is close to the mean shale composition, except for higher contents of Mo, Hg, Pb, Se, Ta, Te, Th, V, and U and lower contents of Ba, Bi, Cd, Co, Re, Sr, and Zn. The results suggest that the change from phosphate sedimentation in aerated environments to anoxic carbonaceous sedimentation was accompanied by changes in the composition and concentration of trace elements in the sediment. Both facies show similar trends of trace element distribution indicative of the stability of the composition of seawater and terrigenous sediment input.     

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.     

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.     

Background levels and baseline values of available heavy metals in Mediterranean greenhouse soils (Spain)

This study determines extractable levels of Cd, Cu, Pb, Zn, Ni and Co in western Almería (Spain) greenhouse surface soil horizons using EDTA solution, which is identified as the fraction available for organisms and plants. It also establishes background levels, geochemical baseline concentration and reference values (RV), and investigates the possible relationships between soil properties and elemental concentrations. The results show that the soil concentration of these extractable heavy metals was high as those reported by other authors for Spanish agricultural soils. The available RV concentrations obtained (mg kg⁻¹) were: Cd 0.17, Cu 1.6, Pb 13.8, Zn 5.0 Ni 1.7 and Co 2.9. Using the upper baseline criterion, 95% of greenhouse soils present a relatively higher content of extractable heavy metals given their Cd and Cu concentration. Significant correlations between total and EDTA-extractable metal levels were found for Zn, Pb, Cu, Cd and Ni. Soil properties also related to heavy metals content, suggesting that Cd, Cu, Pb and Zn are of similar origin and relate to anthropic activities, and implies the same interactions and/or relationships among these metals.     

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.     

滇东下寒武统生物磷块岩的形成机制

显微结构研究表明,广泛分布于滇东地区下寒武统的磷块岩,除少量生物介壳磷块岩外,其它类型的磷块岩(包括菌藻生物磷块岩、内碎屑磷块岩和次生(风化)磷块岩等的颗粒均由磷质菌藻生物组成。从而揭示了菌藻生物磷块岩是磷块岩的基本类型。本文重点论述了生物磷块岩的结构成因分类、时空展布规律,以及滇东磷块岩的菌藻生物成磷—富磷作用,并探讨了菌藻生物磷块岩的形成机制。     

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.     

贵州瓮安陡山沱组磷块岩稀土元素地球化学特征与沉积期后变化

贵州瓮安陡山沱组磷块岩保存了可能是全球最早的后生动物化石 (瓮安动物群 ),对于瓮安动物群出现过程中的古海洋环境重建具有重要科学意义。但必须对成岩后生作用对磷块岩中的稀土元素改造进行评估。通过对贵州瓮安陡山沱组磷块岩的磷质碎屑、磷质和白云质胶结物、磷条带和泥条带等的稀土元素地球化学特征研究,确定沉积期后变化对稀土元素的改造影响不大。上矿层磷块岩沉积期形成的磷质碎屑、成岩期形成的白云质和磷质胶结物具相同的稀土元素配分模式,暗示了沉积期后的改造作用对瓮安陡山沱组磷块岩保存的原生沉积信息影响不大。瓮安陡山沱组磷块岩具有显著的重稀土亏损特征。磷块岩的磷质和白云质胶结物、伴生磷质碎屑、强风化磷块岩相近的ErN/LuN 比值,表明沉积期后的改造作用不是重稀土元素亏损的主要原因。磷块岩的ErN/LuN、LaN/NdN 与Ce/Ce 间的相关性,表明越氧化的沉积环境中,轻和重稀土元素亏损越强。     

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.     

中国南方晚震旦世沉积相及磷块岩的时空分布

本文扼要阐述扬子地台及邻区晚震旦世地层的研究现状,沉积相带(台地相、斜坡相及盆地相)及古地理轮廓、磷块岩的时空分布(包括地理、地层及沉积相的分布)。同时还着重指出了台地边缘及斜坡相带的上部是寻找磷块岩的有利地区。     

More evidence in favour of the biochemical origin of the Mussoorie phosphorite,Kumaon Lower Himalaya,India

Particles of definite skeletal and faecal origin, oncolites and stromatolitic structures from Mussoorie phosphorite, occurring in the Kumaon Lower Himalaya, have been illustrated in the present note with the purpose of providing more evidence in favour of the biochemical mode of origin of these phosphorites.     

Origin of PhosphoriteNodules of Lebedinsky Iron Deposit in Kursk Magnetic Anomaly （KMA） of the Russian Platform

INTRODUCTION TheKurskmagneticanomaly(KMA)coversnear ly120000km2andhasalengthof600kminSE NW direction,withawidthrangingfrom150kmto250 km.TheKMAbasinislimitedbytheDoneskPaleozoic massifinthesouthandthePrecambrianAzovsk podol skupliftinthesouth westanditsnorthernborderis markedbythecrystallinemassifupliftofVaronesh.0 c s TheLebedinskycomplexdepositislocatedinthecentral partoftheRussianplatformbetweenlatitude50°00′and50° 20′north,andlongitude34°00′and39°00′east,inthefron ti…     

Anatomy and origin of a Cretaceous phosphorite-greensand giant, Egypt

Late Cretaceous epicontinental phosphorites, porcelanites/cherts, dark-coloured shales, glauconitic sandstones and bioclastic and fine-grained carbonate rocks in Egypt are examined in terms of their overall depositional and diagenetic framework and stable isotopic and organic geochemical characteristics. Two main depositional realms are interpreted and correlated through sequence stratigraphic analysis: (1) a shallow hemipelagic environment accompanying initial stages of marine transgression and conducive to the formation of organic carbon-rich shales, biosiliceous sediments and thick phosphorites, and (2) a relatively high energy depositional regime accompanying sea-level fall during which deltas advanced, glauconites were reworked seaward and prograding oyster banks became periodically exposed to episodes of fresh water diagenesis, thereby promoting solution-collapse phenomena in associated cherts. Lenticular to massive phosphorites are viewed as the result of current winnowing and concentration of authigenic grains initially precipitated in associated reducing shales and biosiliceous sediments. In eastern Egypt the phosphorites form winnowed lag layers, some of which may have been redeposited down slope in structural lows. In the west, these sands were concentrated into giant phosphorite sand waves built by reworking of penecontemporaneously deposited phosphatic muds during marine transgression. Carbon isotopic results substantiate interpretations from modern deposits for limitation of phosphate mineral precipitation with depth in sediments as a result of lattice poisoning. However, direct desorption of phosphorus to pore waters from detrital iron-oxyhydroxide phases also may have been important in the Cretaceous setting, the iron reduced in this process being available for incorporation in glauconites. The main locus for authigenic glauconite precipitation appears to be where iron fluxes from regions of lateritic weathering were highest and near the boundary between oxygenated and reduced waters. This study suggests a model for the common coexistence of glauconites and phosphorites in the geological record. Although upwelling is often advocated as the origin of nearly all giant phosphorite deposits, we suggest that some of these may have been strongly influenced by fluvially derived phosphorus borne on particulates and desorbed from these compounds upon flocculation and/or reduction in bottom waters or pore waters.     

朝阳磷矿磷块岩的类型和成因特征

朝阳磷矿的磷块岩有五种类型,即泥晶磷块岩、球粒磷块岩、鲕粒磷块岩、内碎屑磷块岩和细晶磷块岩。其中内碎屑磷块岩占优势。磷酸盐岩沉积在海退旋回中,是处于深水向浅水过渡的层位。磷块岩的沉积环境主要是隆起附近的浅水带。