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.     

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.     

Francolite geochemistry—compositional controls during formation,diagenesis, metamorphism and weathering

Francolite in unaltered Tertiary phosphorites is highly substituted with about 1.2% Na, 0.25% Sr, 0.36% Mg and 2.7% SO₄ within the structure in substitution for Ca and PO₄. These substitutions reflect the composition of the solution from which francolite forms and are not influenced by the mechanism, rate or redox conditions of formation. The remarkably constant composition for a wide range of samples reflects the relative constant composition of sea water, during Tertiary times. Francolite in sulphate-reducing sediments forms in an uppermost zone where bioturbation maintains the concentrations of Na, Sr, Mg and SO₄ at sea water concentrations. The structura-CO₂ content of unaltered francolites vary from 1.4% to 6.3%, in response to variations in pH. The maximum level of carbonate substitution is limited by the disruption of the francolite structure at levels above 6.3% CO₂. For the samples considered here F/P₂O₅ ratios vary with X-ray CO₂ contents showing that PO₄^3? is replaced by (CO₃^2? + F?) and not by CO₃^2? alone. In Phosphoria Formation francolite the Na/P₂O₅ ratios and X-ray CO₂ contents show areal trends related to burial depth and thermal metamorphism. These two processes together with weathering and fresh water diageneses explain all observed variation in francolite composition.     

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.     

Pétrographie et géochimie comparées des pellets phosphatés et de leur gangue dans le gisement phosphaté de Ras-Draâ (Tunisie). Implications sur la genèse des pellets phosphatés

Paléocène-Early Eocene phosphate outcrop in the Ras-Draâ deposit (Tunisia) comprises alternances of P-rich strata (P₂O₅ ≥ 18%) and P-poor ones (P₂O₅ ≤ 2%). In phosphate rich strata, P is concentrated in rounded grains—so-called pellets—(28% ≤ P₂O₅ ≤ 38%) embedded in a matrix—so-called exogangue—much poorer in P (P₂O₅ # 7%) than pellets. The study of pellets (whose size lies mainly between 100 and 500 μm), of their surrounding matrix and of poorly phosphatic sediments, interlayered between the phosphatic strata, has been performed by optical microscopy and various chemical analyses, ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectroscopy) and punctual chemical analyses by EDS (Energy Dispersive Spectroscopy). Mineralogical and chemical studies of the Tunisian phosphatic pellets show that the basic mineralogical component of these grains is carbonate-fluor-apatite, or francolite. The structural formula of a representative specimen of francolite in the basin is as follows: (Ca_4.63Mg_0.13Na_0.22)(PO₄)_2.51(CO₃)_0.48(OH_0.77F_0.23). The mineralogy of the constituents of the sediment surrounding pellets comprises carbonates, clays, silica (opal, quartz). Microscopic observations of Ras-Draâ phosphorites, added to geochemical results, establish that pellets are small bodies, allochtonous to their matrix and whose composition is independent of that of this matrix. Fecal cylindrical bodies and subspherical pellets, the latest being supposed to proceed from the fecal bodies by fragmentation, are considered to have been formed by fishes, as P-rich and organic matter-rich faeces. These faeces turn out to be resistant to mechanical dispersion and to chemical diffusion of soluble elements from and in direction of sea water. This closeness is responsible for the strong reducing conditions having prevailed inside and during the pellets diagenesis.     

Mineralogical and geochemical studies on Abou-Sabouna phosphorites (Mahamied-Sharawna), upper Egypt,A. R. E.

Summary The Phosphate Formation of the Campanian-Maestrichtian in the Abou-Sabouna-Mine on the eastern side of the Nile Valley near Mamied was investigated mineralogically and geochemically. The phosphorite deposits are of the bedded type, containing collophane, francolite, smaller amounts of quartz, calcite, geothite and chlorite, rarely zircon. The phosphate material contains F^– (F/P₂O₅=0.089–0.094), as is characteristic for francolite.The phosphorites were deposited in a shallow marine environment with strong agitation. Diagenetic processes have changed the mineralogical and geochemical composition. Silification can be observed during diagenesis associated with accumulation of hematite.

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Mineralogische und chemische Untersuchungen an Phosphoriten von Abou-Sabouna (Mahamied-Sharawna), Ober-Ägypten, Arabische Republik Ägypten

Zusammenfassung Die Phosphatformation des Campan-Maastricht der Abou-Sabouna-Mine, östlich des Niltales bei Mamied, wurde mineralogisch und geochemisch untersucht. Die Phosphatlagerstätte ist von lagerartigem Typ; sie enthält Collophan, Frankolith, untergeordnet Quarz, Calcit, Goethit und Chlorit, als Seltenheit Zirkon. Im Phosphat ist F^– mit einem F/P₂O₅-Verhältnis von 0,089 bis 0,094 nachzuweisen, was für Frankolith charakteristisch erscheint.Die Phosphorite wurden in einem flach marinen, stark durchbewegten Milieu abgesetzt. Diagenetische Prozesse haben die mineralogische und geochemische Zusammensetzung durch Silifizierung und Hämatitbildung verändert.

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With 4 Figures     

Petrography, chemistry and genesis of phosphorite concretions in the Eocene Umm Rijam Chert limestone Formation, Ma'an area, south Jordan

Phosphorite concretions are recorded for the first time within the lower part of the Umm Rijam Chert Limestone Formation (Eocene) in the Ma'an area, southern Jordan. The phosphorite concretions are typically hosted and encountered as individual layer in moderately lithified sediments of marl, chalk and chalky marl. The phosphorite concretions are present in thin layer (10–30 cm thick). They are localized on a hardground surface that formed as a result of cementation of soft ground by bioclastic materials. Light grey and brownish to black colors are encountered with isometric, ellipsoid, elongated, subangular to subrounded phosphorite concretions (up to 6 cm in length). Most of the phosphorite concretions preserve bioturbation structures; they also include fecal pellets of various sizes. The main biogenic components are fragments of macrofossils (bivalves) and microfossils (planktonic foraminifera) in different proportions. Petrographic examinations reveal that the phosphorite concretions are composed of cryptocrystalline apatite that characteristically appears in cross-polarized light almost as isotropic phosphate and minor anisotropic phosphate. Apatite and calcite are the main mineral constituents of the phosphorite concretions identified by XRD. The apatite is identified as francolite (carbonate-flour-apatite). Chemical analyses of the phosphorite concretions using X-ray florescence indicate that the P₂O₅ content ranges from 18.8 to 31.19%, whereas SEM–EDS analyses indicate that the phosphorus proportion is around 14% by volume. It could be argued that the phosphorite concretions were transported after being reworked, or were derived from carbonate and chalk pebbles that were later phosphatized and subjected to erosion, forming residual lag deposit along the hardground surface.     

Chemical variability in francolites from Israeli phosphorite macrograins

The chemical composition (up to 7 elements) of francolite in 64 samples of Israeli phosphorites from 7 fields was determined. Samples comprising mainly skeletal macrograins contain, on the average, 1.5% less P₂O₅, than those with other types of macrograins (mostly pelletal). Average CO₂ in the skeletal variety is 4%, against 3% elsewhere. There is a strong positive correlation between Na and CO₂, and a strong negative one between Mg and P₂O₅. Of the principal components explaining more than 95% of the chemical variation, the first, which opposes phosphate to carbonate and to sodium, differentiates between types of macrograins; the second, based on calcium and sodium not coupled with carbonate, differentiates between phosphorite fields. This is clearly seen from the graph (Fig. 6) obtained by correspondence-factor analysis. The difference between skeletal and other magrograins could be due to origin or to diagenetic changes, which include francolitisation of carbonate hydroxyapatite.     

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。     

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.     

New occurrence of potential phosphate resource in northeast Jordan

An exploration program aided by field investigation, exploration drilling, detailed sampling, lithological and petrological studies, geochemical investigation, and resource calculation leads to the discovery of a potential phosphate resource in northeast Jordan close to the international border with Saudi Arabia and Iraq. The studied phosphate is of the Middle Eocene age that belongs to the Wadi Shallala Formation. It is equivalent to the phosphate deposits recorded in the lower part of the Umm Wual Formation in the Turayf region of Saudi Arabia and the Eocene Ratga Formation in the Ethna phosphate deposit west of Iraq. The phosphorites in the region are broadly similar in mineralogical composition and geochemical affinities. X-ray diffraction indicates the presence of francolite with variable amounts of calcite and quartz. Most samples consist of phosphate clasts embedded in carbonate and silica matrix and cement. P₂O₅ content is up to 32.3 % with an average equal to 18.6 %. The impurity is caused by the presence of variable amounts of SiO₂ and CaO. The F% and F/P₂O₅ ratio in studied phosphates is lower compared with that in phosphates from Jordan and Saudi Arabia. The geological and geochemical results were integrated for resource estimation. Three high-grade phosphate layers with ≥23 % P₂O₅ were considered in the calculations. The phosphate resource is classified as an inferred resource. The total volume of the resource is about 649 million tons. The average P₂O₅ content is 24.57, and the stripping ratio is 1:5.8.     

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.     

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.     

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。     

Geochemical, mineralogical and isotopic signatures of the Semikan, West Kasrık “Turkish” phosphorites from the Derik–Mazıdağı–Mardin area, SE Anatolia

The geochemistry and mineralogy of a condensed section, ~6 m thick of the West Kasrik member (Coniacian–Santonian) near the uplifted northern flank of the Mardin–Derik anticline (south-eastern Turkey) was studied. The only deposit exploited in Turkey is found in this area. The sediment textures as well as the mineralogical and the geochemical results collectively suggest that these recycled phosphorites accumulated in areas of intensive very early diagenesis of the sediments in highly oxic bottom waters, and almost no detrital apport. The total concentration of redox-sensitive trace metals is very low (<600 μg/g); in addition the structural CO₂ and F/P₂O₅ are unusually high (~5 wt % and 0.14, respectively). REE distribution shows a clear “seawater” pattern with a strongly negative Ce-anomaly (0.20 ± 0.02) and heavy REE enrichment (Lu_N/La_N = 1.50 ± 0.12), however their total concentration is very low. The low REE contents, quite unexpected in recycled phosphorites, are explained by the scarcity of terrigenous components which leads to minimal incorporation of REEs from detrital clastic phases in the CFA fraction. Weathering previously suggested as responsible for the high P enrichment of the Mazidagi phosphorites is rather improbable in the samples we studied, in view of their high structural CO₂, high F/P₂O₅, high (La/Nd)_N and (La/Sm)_N ratios, and high Sr/P and Ca/P of separated CFA fractions that all negate post-depositional weathering. More likely, the high P enrichment of some rocks (P₂O₅ content reaches 34%) was produced by sedimentary and early diagenetic processes acting in oxygenated areas of starved sedimentation on and around tectonic highs.     

FeO*-Al2O3-TiO2-Rich Rocks of the Tertiary Bana Igneous Complex, West Cameroon

FeO*‐Al₂O₃‐TiO₂‐rich rocks are found associated with transitional tholeiitic lava flows in the Tertiary Bana plutono‐volcanic complex in the continental sector of the Cameroon Line. These peculiar rocks consist principally of iron‐titanium oxides, aluminosilicates and phosphates, and occur as layers 1–3 m thick occupying the upper part of lava flows on the southwest (site 1) and northwest (site 2) sites of the complex. Mineral constituents of the rocks include magnetite, ilmenite, hematite, rutile, corundum, andalusite, sillimanite, cordierite, quartz, plagioclase, alkali feldspar, apatite, Fe‐Mn phosphate, Al phosphate, micas and fine mixtures of sericite and silica. Texturally and compositionally, the rocks can be subdivided into globular type, banded type, and Al‐rich fine‐gained massive type. The first two types consist of dark globule or band enriched in Fe‐Ti oxides and apatite and lighter colored groundmass or bands enriched in aluminosilicates and quartz, respectively. The occurrence of andalusite and sillimanite and the compositional relations of magnetite and ilmenite in the FeO*‐Al₂O₃‐TiO₂‐rich rocks suggest temperatures of crystallization in a range of 690–830°C at low pressures. The Bana FeO*‐Al₂O₃‐TiO₂‐rich rocks are characterized by low concentrations of SiO₂ (25–54.2 wt%), Na₂O + K₂O (0–1%), CaO (0–2%) and MgO (0–0.5%), and high concentrations of FeO* (total iron as FeO, 20–42%), Al₂O₃ (20–42%), TiO₂ (3–9.2%), and P₂O₅ (0.26–1.30%). TiO₂ is positively correlated with Al₂O₃ and inversely correlated with FeO*. The bulk rock compositions cannot be derived from the associated basaltic magma by crystal fractionation or by partial melting of the mantle or lower crustal materials. In ternary diagrams of (Al₂O₃)?(CaO + Na₂O + K₂O)?(FeO*+ MnO + MgO) and (SiO₂)?(FeO*)?(Al₂O₃), the compositional field of the rocks is close to that of laterite and is distinct from the common volcanic rocks, suggesting that the rocks are derived from lateritic materials by recrystallization when the materials are heated by the basaltic magmas. A hydrothermal origin is discounted because the rocks contain high‐temperature mineral assemblages and lack sulfide minerals. It is proposed that the FeO*‐Al₂O₃‐TiO₂‐rich rocks of the Bana complex were formed by pyrometamorphism of laterite by the heat of basaltic magmas.     

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.     

Analytical Constraints on the Measurement of the Sulfur Isotopic Composition and Concentration of Trace Sulfate in Phosphorites: Implications for Sulfur Isotope Studies of Carbonate and Phosphate Rocks

The aim of this study was to evaluate the existing methods for extracting trace sulfate from francolite and measuring its concentration and sulfur isotope composition. Phosphatic rocks were chemically and thermally treated to remove non‐structural SO₄^2? in francolite, which would otherwise be inadvertently included in geochemical analyses of the structurally‐bound sulfate. Acetic acid (10% v/v) proved to be effective in removing calcite, dolomite and ankerite without affecting francolite. To remove all ‘easily’ soluble sulfates, such as Ca‐sulfates and adsorbed sulfate, rinsing with 10% v/v NaCl had to be repeated several times for most samples. For subsequent S isotope determination sample combustion at 600 °C was found to be an efficient way to remove non‐francolite S‐bearing phases. From a number of SO₄^2? detection methods tested, ICP‐AES proved to be the most accurate. For francolite‐sulfate recovery, our recommended protocol involved repeated rinsing of powdered phosphorites with 10% NaCl as well as NaOCl, and testing of the filtrate for SO₄^2? in each wash. If only S isotope compositions are needed, combustion at 600 °C with a subsequent de‐ionised water rinse could be undertaken instead of repeated NaOCl rinsing for studies of both francolite and carbonate. Re‐analysis of previously published data, using the new protocol, provided evidence that the use of this protocol considerably improves data quality.     

Dolomitization,gypsum calcitization and silicification in carbonate–evaporite shallow lacustrine deposits

This paper describes and interprets the mineral and facies assemblages that occur in carbonate–evaporite shallow lacustrine deposits, considering the importance of the processes pathway (i.e. dolomitization, gypsum calcitization and silicification). The Palaeogene deposits of the Deza Formation (Almazán Basin, central‐northern Spain) are selected as a case study to determine the variety of physicochemical processes taking place in carbonate–evaporite shallow lakes and their resulting diagenetic features. Dolostones are the predominant lithology and are composed mainly of dolomite with variable amounts of secondary calcite (5 to 50%), which mainly mimic lenticular gypsum (pseudomorphs). Five morphological types of dolomite crystal were identified as follows: dolomite tubes, dolomite cylinders, rhombohedral dolomite, spheroidal and quasi‐rhombohedral dolomite, and cocoon‐shaped dolomite. The dolomite cylinders and tubes are interpreted as the dolomitized cells of a widespread microbial community. The sequence of diagenetic processes started with growth of microlenticular interstitial gypsum in a calcareous mud deposited on the playa margin mudflats, and that sometimes included microbial sediments. Immediately following growth of gypsum, dolomite replaced the original calcite (or possibly aragonite) muds, the microbial community and the gypsum. Partial or total replacement of gypsum by dolomite was related mainly to the biomineralization of endolithic microbial communities on gypsum crystals. Later calcitization took place under vadose, subaerial exposure conditions. The development of calcrete in distal alluvial settings favoured the release of silica and subsequent silicification on the playa margin mudflats. Stable isotope compositions of calcite range from ?9·02 to ?5·83‰ δ¹³C_PDB and ?7·10 to 1·22‰ δ¹⁸O_PDB; for the dolomite, these values vary from ?8·93 to ?3·96‰ δ¹³C_PDB and ?5·53 to 2·4‰ δ¹⁸O_PDB. Quartz from the cherts has δ¹⁸O_SMOW values ranging from 27·1 to 31·1‰. Wide variation and relatively high δ¹⁸O_SMOW values for dolomite indicate evaporitic and closed hydrological conditions; increased influx of meteoric waters reigned during the formation of secondary calcite spar.     

The fluorescence sideband method for obtaining acoustic velocities at high compressions: application to MgO and MgAl2O4

Sound velocities to 37 GPa have been obtained for MgO based on new sideband measurements and sound velocities have been calculated for MgAl₂O₄ to 11 GPa based on previous sideband measurements. The basic principles of the sideband fluorescence method are presented and it is shown that the vibrational mode energies in the sidebands are independent of the impurity cation and represent modes of the undisturbed lattice. Furthermore, it is shown that the acoustic modes represent spherically averaged velocities by comparison of these results to the directional information provided by ultrasonic data. The resulting pressure derivatives of the elastic moduli for both materials are in excellent agreement with those derived from lower-pressure ultrasonic data. The velocities over the pressure range of this study may be described by the following relations: for MgO, v_s=6.05 (1)+0.0381 (13) · P-3.6(4) × 10^?4 · P² and v_P=9.70(2)+0.0704(20) · P-5.6(6)×10^?4 · P² and for MgAl₂O₄, v_s=5.49(5)+0.001(11) · P and v_P = 9.785 (11)+0.047 (5) · P-0.0010(5) · P² where the pressure P is in GPa. Velocity is linear with density over the pressure range of this study.