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.     

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.     

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     

Structural CO2 in the Apatite of the Late Cretaceous Phosphorite Resources in Egypt: Effect on the Crystal Chemistry and Geologic Implications

Abstract: Phosphorite deposits in Egypt, known as the Duwi Formation, are a part of the Middle East to North Africa phospho‐genic province of late Cretaceous to Paleogene age. Based on the petrographical observation, the phosphatic grains in the phosphorites are classified into phosphatic mudclasts and phosphatic bioclasts. Both of them are composed of francolite. The structural CO₂ contents in the francolite range from 3.3 to 7.2 % with an average of 5.3 %. Results indicated that the substitution with CO₃^2‐ of PO₄^3‐ in the francolite decreases the unit cell volume and a‐cell dimension, and increases the c/a ratio. Effect is more obvious in the a‐cell dimension; therefore, it is more significant in distinction between the different apatite species. Lack of covariance between structural CO₂ contents in the francolite and the carbonate minerals contents may render the supposition that the phosphorites formed as a result of replacement of preexisting calcareous sediments is doubtful. Similarity in CO₂ content in both weathered and fresh samples indicates that the structural CO₂ content in the phosphorites is not affected by weathering, and reflects the conditions and CO₂ concentration of the depositional environment. Similarity in mineralogy and CO₂ contents in the different phosphatic grains and higher CO₂ content in the Egyptian phosphorites compared with the authigenic phosphates of Peru margin, which formed by the same mechanism as the Duwi phosphorites, suggest that the phosphatic grains in the Duwi Formation were francolitized during diagenesis by introducing CO₂ from the surrounding pore water and diagenesis took place at an elevated temperature. Scattered values of structural CO₂ contents suggest the reworking origin of the phosphatic grains in the late Cretaceous phosphorites in Egypt.     

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.     

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.     

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.     

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.     

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.     

昆阳磷矿磷块岩的矿物组成

昆阳磷矿是我国下寒武统最大的磷块岩矿床之一,矿层赋存于下寒武统渔户村组的中谊村段地层中(罗惠麟等,1982),矿层有上、下两层,分别称之为“上磷层”和“下磷层”,中间为一“白泥层”(含磷粘土页岩)分隔(Yeh Lien-tsun et al.,)。含磷岩系的岩性序列特征见图5。罗惠麟等认为,本段地层均为台凹相沉积,其中“下磷层”的形成环境为潮下低能及间歇性高能带,“白泥层”为潮下低能带,“上磷层”为潮下高能带,再往上则向潮间坪过渡。本文研究磷块岩的矿物组成,主要是矿石矿物磷灰石和粘土矿物的特点,并讨论磷灰石成份同矿石类型和形成环境等问题。     

Animals and Mineralization of Phosphorus: Ore-Forming Mechanism of Insular Phosphorites1

Abstract Phosphorite, or guano, or insular phosphorite, commonly containing 10-35% P₂O₅, is one of the sources of phosphatic fertilizer. Taking the modern insular phosphorite on the Xisha Islands as an example, this paper discusses the ore-forming mechanism of phosphate and the important contribution made by animals to this process. The phosphorite occurs in the middle part of carbonate sand cays of coral reef surrounded by longshore sandbanks, which assumes a dish-shape. The surface of the cays is covered by unconsolidated guano. The phosphorite, yellowish brown to dark brown, is made up of thick-bedded sand and gravel cemented by collophanite; and partly replaced by carbonate apatite. The mechanism of mineralization is as follows: The average content of phosphorus in the sea water is only 0. 07 ppm, but through the sea food. chain concentration, phosphorus content may become higher. The phytoplanktons, as producers, suck up phosphorus out of sea water. The primary consumers, zooplanktons, obtain phosphorus by eating phytoplanktons, then they are followed by the second and third consumers. Sea birds living on fish, as the third consumers, concentrate and transport the phosphorus to the carbonate sand cays. Finally layers of guano are deposited under the arbores. Under the tropical climatic conditions with high temperature and plentiful rainfall, soluble matters are leached out of the guano and infiltrated into deeper horizon. In alkaline groundwater with pH greater than 7. 0, the phosphoritization takes place, bioclastics are cemented and replaced by collophanite or carbonate apatite. Finally, the phosphorus is fixed and phosphate formed.     

The geochemical characteristics of aqueous rare-earth elements in shallow karst groundwater in Guiyang City,China

Fifty-seven shallow groundwater samples were collected from Guiyang karst basin, China, to analyze the aqueous rare-earth elements in low-water seasons and it is shown that the total amount of rare-earth elements (ΣREE) in karst groundwater is exceedingly low compared with that in carbonate rocks or weathering crusts of carbonate rocks, and ranges from 0.01 to 0.43, from 0.03 to 0.27, from 0.03 to 0.19 and from 0.05 to 1.38 μg·L-1 for dolomite, dolomitic & limestone, limestone and clastic rock aquifer, respectively. Both distributions and contents of rare-earth elements (REE) in karst groundwater reflect the lithology of host rocks or weathering crusts of carbonate rocks through which groundwater flows. The chondrite-normalized patterns show a non-flat profile with higher enrichment of slightly light rare-earth elements (LREE) than heavy rare-earth elements (HREE), prominent fractionation between LREE and HREE, negative Ce anomalies and negative or positive Eu anomalies. There is more obvious fractionation between LREE and HREE in groundwater than that in carbonate rocks and their weathering crusts due to high contents of HCO3? and PH in groundwater. In shallow karst groundwater, REE(CO3)n2n-3 (n=1 and 2) is the main inorganic species of REE. But for a clastic rock aquifer, both REESO4+ and REECO3+ are the main inorganic species of REE. Species of REE in groundwater is closely associated with the hydrochemical type of groundwater which is predominated by the lithology of host rocks, groundwater-rock interaction and weathering-pedogenesis of carbonate rocks.     

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.     

磷块岩的胶结作用

磷块岩胶结物有泥质、硅质、磷质和碳酸盐质4种,共形成19种胶结结构,其中尤以磷泥晶环边结构、等厚纤状环边结构、似重力式结构、磷质纤状环边叠加云质亮晶充填结构特征突出,具有指示沉积成岩环境的意义。4种类型的胶结物在剖面和平面上的演变与水体深度和沉积成岩环境有关,而胶结作用的地球化学特征,既是磷块岩的环境指示,又反映微生物的影响状况。     

中国南方风化磷块岩研究

中国南方风化磷块岩中的风化磷矿的自然类型可分为两类七种型式，其中以“原位面型风化磷矿”和“位移溶洞砂砾磷矿”为主。风化磷矿是由其原矿的自身特性与外部适宜条件（水文地质条件为主导）综合作用的产物。根据碳酸盐、磷酸盐矿物分解、淋失程度可划分为弱风化、风化、强风化三个阶段。可用直接法、间接法和数学法３类共１３种方法加以判别     

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.     

Formation of modern dolomite in hypersaline pans of the Western Cape,South Africa

Authigenic calcite and dolomite and biogenic aragonite occur in Holocene pan sediments in a Mediterranean‐type climate on the western coastal plain of South Africa. Sediment was analysed from a Late Pleistocene coastal pan at Yzerfontein and four Holocene inland pans ranging from brackish to hypersaline. The pans are between 0·08 and 0·14 km² in size. The δ¹⁸O_PDB values of carbonate minerals in the pan sediments range from ?2·41 to 5·56‰ and indicate precipitation from evaporative waters. Covariance of total organic content and percentage carbonate minerals, and the δ¹³C_PDB values of pan carbonate minerals (?8·85 to ?1·54‰) suggest that organic matter degradation is a significant source of carbonate ions. The precipitation of the carbonate minerals, especially dolomite, appears to be mediated by sulphate‐reducing bacteria in the black sulphidic mud zone found in the brine‐type hypersaline pans. The knobbly, sub‐spherical texture of the carbonate minerals suggests that the precipitation of the carbonate minerals, particularly dolomite, is related to microbial processes. The ⁸⁷Sr/⁸⁶Sr ratios of pan carbonate minerals (0·7108 to 0·7116) are slightly higher than modern sea water and indicate a predominantly sea water (marine aerosol) source for calcium (Ca²⁺) ions with relatively minor amounts of Ca²⁺ derived from the chemical weathering of bedrock.     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

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。     

Pb-Pb age of sedimentary phosphorite reworking in Lower Riphean carbonate sediments,the Satka Formation of Southern Urals

The mineral composition and U-Pb and Rb-Sr systematics of phosphorites from the Satka Formation of Lower Riphean carbonates, the Burzyan Group of Southern Urals, are studied. Phosphorites occurring as small lenses between stromatolite layers are composed largely of fluorapatite with admixture of detrital quartz, feldspars, illite, and chlorite. Phosphorite samples have been subjected to stepwise dissolution in 1 N (fraction L-1) and 2 N (fraction L-2) HCl. As is established, the maximum apatite content is characteristic of fraction L-1, while fraction L-2 is enriched in products of dolomite and sulfide dissolution and in elements leached from siliciclastic components. The Sr content in the Satka apatites (280–560 ppm) is substantially lower as compared with that in unaltered marine apatite. The ⁸⁷Sr/⁸⁶Sr “initial ratio in the phosphorites studied (0.71705–0.72484) and host dolomites from the lower part of the Satka Formation is significantly higher than in the Early Riphean seawater that indicates a reset of the Rb-Sr original systems in sediments. The Pb-Pb age of 1340 ± 30 Ma (MSWD = 6.4) estimated based on 7 data points characterizing fractions L-1 and L-2 is younger than the formation time of overlying Burzyan sediments, being consistent, within the error range, with date of the Mashak rifting event recorded at the Early-Middle Riphean boundary. The comparative U-Pb characteristics of two soluble fractions (L-1 and L-2) and silicate residue of phosphorites show that epigenetic redistribution of Pb and U was characteristic of the phosphorite horizon only. The initial Pb isotope composition and μ (²³⁸U/²⁰⁴Pb) estimated according to model by Stacey and Kramers for the early diagenetic fluids in carbonate and phosphate sediments of the Satka Formation suggest that they were in isotopic equilibrium with erosion products of the Taratash crystalline complex.