Rare Earth Elements Compositions and Genesis of Xinhua Large-Scale Phosphorite Deposit in Western Guizhou, China

Zhijin County in Western Guizhou is one of the most important production areas of phosphorites in China. In order to investigate genesis of the phosphorites, their REE compositions were analyzed by using inductively coupled plasma emission mass spectrometry (ICP-MS) method. For comparison, phosphorites from the Lower Cambrian black rock series in Southern China, such as Zunyi in Guizhou and Zhangjiajie in Hunan Province, were also analyzed. The analytical data show that: (1) Xinhua phosphorites possess a quite high and greatly varied total rare earth elements (ΣREE), which varying between 164.23×10-6 and 1395.01×10-6 with average of 642.54×10-6, remarkable differentiation between light (LREE) and heavy rare earth elements (HREE), and the ΣLREE/ΣHREE ratios varying between 5.04 and 6.52. The ΣREE and ΣLREE/ΣHREE ratios of the Zunyi and Zhangjiajie phosphorites are 156.69×10-6～637.41×10-6 with average of 431 75×10-6 and 3.17～6.95 with average of 4.37 respectively; (2) All the phosphorites from Xinhua, Zunyi and Zhangjiajie show remarkable negative Ce anomalies. Besides, the Xinhua phosphorites possess lower δCe, which varying between 0.26 and 0.53 with average of 0.35, while δCe of the Zunyi and Zhangjiajie phosphorites are 0.30～0.66 with average of 0.47, suggesting that all of the phosphorites are typical marine sediments deposited mainly in ancient peri-continental seas, and the depositional position of the Xinhua phosphorite might be deeper; (3) Most phosphorites from Xinhua, Zunyi and Zhangjiajie possess unremarkable positive Eu anomaly, and only a few of samples show obvious ones. The δEu varies between 0.98 and 2.4, suggesting that hot (>200 ℃) and strong reductive hydrothermal fluids might have been involved in genesis of the phosphorites; (4) The Xinhua phosphorite is relatively depleted in HREE, and LaN/NdN and δY of most samples are >1 and >1.5 respectively. Besides, there exists no correlation between δY and δCe, suggesting that the phosphorite was subjected to quite strong weathering and leaching processes, and catagenesis do not greatly modify its REE compositions.

Phosphorite generative processes around the Precambrian-Cambrian boundary in South China: An integrated study of Mo and phosphate O isotopic compositions

Large phosphorite deposits in Central Guizhou,China,were formed around the Precambrian/Cambrian boundary(PC/C),including the Ediacaran(Doushantuo stage)and early Cambrian(Gezhongwu stage).Among them,Gezhongwu phosphorite from Zhijin are enriched in rare earth elements(REE)plus yttrium(REY),reaching 3.503 million tons.Although phosphorites have attracted great attention,the specific sources P and REY remained unclear.To determine the P and REY sources and establish a phosphogenic model of PC/C phosphorite,we present an integrated dataset of Mo and phosphate O isotopes for the first time,along with carbonate C and O isotopes,geology,petrology,and geochemistry.In all samples,d18Op,Y/Ho,and Zr/Hf decreased from the Ediacaran to the early Cambrian,indicating increased terrigenous weathering fluxes while decreased upwelling water input.Furthermore,terrigenous weathering delivery significantly elevated marine REY concentrations in the Cambrian in Zhijin.The Ceanom and d98/95Mo suggest that seawater was oxidized in the later Ediacaran and became entirely oxic in the early Cambrian.The positive feedback between oxygen levels in atmosphere and primary productivity caused progressive oxygenation in ocean-atmosphere system and enable phosphorites to be formed by different mechanisms.Results show that the Lower Doushantuo consist of abiotic intraclasts and exhibited“seawaterlike”REY types,indicating abiological and mechanical reworking phosphogenesis.The Upper Doushantuo and Gezhongwu Formation contained mainly microbial debris and abiogenic intraclasts,and exhibit “hat-shaped”REY plots,suggesting microbially mediated phosphogenesis.Based on this data set,we developed a phosphogenic model illustrating formation of these two phosphorite deposits,wherein the Lower Doushantuo phosphorite formed through the reworking of pre-existing phosphatic sediments in anoxic and abiotic ocean,whereas the Upper Doushantuo and Gezhongwu phosphorite formed via microbial metabolisms in oxic and biotic conditions.Our study has implications on the PC/C phosphorite generative processes,as well as paleoenvironmental conditions.

Separation and Enrichment of Rare Earth Elements in Phosphorite in Xinhua,Zhijin,Guizhou

The phosphorite ores-deposits rich in rare earth elements(REE) in Zhijin, Xinhua, Guizhuo occurs in the early Cambrian Meishucun and at the bottom part of Qiongzhusi stage (the upper layer of phosphorites), belonging to Yangzi stratum section. The living creature scraps was proved existent in dolomitic-phosphorites by experiments, The REE could be extracted to provide the worthy data for the further using. Adopting the HNO3 to extract REE, through the ion exchange method, the REE recovery rate could be reached 85.44%, having certain reference value.

Rare Earth Elements in Zhijin Phosphorite and Distribution in Two-Stage Flotation Process

Zhijin phosphorite is one of super large-scale medium-low grade and REE-bearing phosphorite deposit in Southwest of China. Previous investigations had revealed that this deposit contained appreciable amounts of rare earth elements (REE) reaching up to 1300 μg·g-1. In this paper, REE contents and existing state in single collophanite and dolomite mineral were further analyzed by ICP-MS and EPMA-1600 Electric Probe methods. The results indicated that REE content of collophanite was far more than that of dolomite, and increased with an increase of phosphor. There existed independent minerals of REE in single collophanite mineral, such as cerianite and monazite, but the amount of them was extremely little. No independent mineral of yttrium was found in this investigation. Presumedly, REE and yttrium were present in the form of ions in the lattices of collophanite. Based on above investigation, the two-stage reverse flotation technology was carried out to see the distribution of REE in flotation process. It was found that REE was mainly enriched in phosphate concentrate and recovered in the rough stage flotation. REE recovery of concentrate increased with an increase of P2O5 content and P2O5 recovery of concentrate. Under the optimum flotation condition, REE recovery was 79.25% in the rough stage flotation and 9.94% in scavenging flotation.

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

Phosphorite has become increasingly important as the raw material for phosphatic fertilizer. Phosphorite nodules are widespread in the Kursk complex deposit (Russian platform). Genesis of these nodules has long been a matter of debate, and this has hampered understanding of the mechanism and controls in the formation of the nodules. In this paper, we report the petrographical, mineralogical, and geochemical data of the Lebedinsky phosphorite nodules. Petrographic study reveals complex phosphatic cement resulting in the replacement of apatite minerals around quartz grains. The main mineral composition consists of quartz, phosphate minerals (apatite, francolite mainly), feldspar, iron hydroxides and carbonate minerals. These results, when combined with available data, are used to address the origin of the phosphorite nodules. The nodules are characterized by the universal presence of biogenic and chemical signatures which is phosphorus crown around crystal grains. The structure of the nodules is massive. Their texture is depicted by basaltic cement and concretion, which consists mainly of apatite and its varieties, with general formula: Ca_10 (PO_4, CO_3) 6(F,OH,Cl). Variation of mineralogy appears dependent on geological setting. Microscopic observations of biogenic fossils in Lebedinsky phosphorite favor a chemical and biogenic origin of phosphorites. Weathering has been suggested to be capable of liberating as much as 20 %-35 % P_2O_5 from sedimentary rocks. Previous investigations demonstrate that weathering of the Proterozoic substratum was the main cause in the formation of Fe, Mo, Mn, Pb, Zn, and P in the Russian platform. We therefore suggest that both weathering and biochemical processes have been positive in the formation of the Lebedinsky phosporite nodules. However, whether continental weathering or oceanic bio-chemical processes are more relevant in the phosphorite accumulation remains undetermined.

Enrichment characteristics and sources of the critical metal yttrium in Zhijin rare earth-containing phosphorites, Guizhou Province, China

Yttrium(Y)is a critical metallic element that is used widely in modern scientific,technological,and industrial applications.Phosphorites in the Zhijin area of Guizhou Province,China,are famous for Y enrichment,but the enrichment characteristics and sources remain unclear.Previous studies suggested that the sources of rare earth elements(REEs,La-Lu)and Y(REYs,La-Lu+Y)were related to hydrothermal deposition.However,this study presents evidence refuting that hypothesis,with major and trace elemental data collected with quadrupoleinductively coupled plasma-mass spectrometry(Q-ICPMS)analysis.These data show that Y in Zhijin REYscontaining phosphorites has a normal distribution and is particularly enriched relative to other REYs.The Y enrichment degree is different at different∑REY intervals.Specifically,the Y enrichment degree is higher at lower∑REY values and lower at higher∑REY values.The REYs-containing phosphorites show features of primary phosphorites.Both REEs and Y have good correlations with P2 O5 in the phosphorites with low REYs contents(total REYs<535 ppm),whereas at high REYs contents(total REYs>535 ppm),REEs have a good correlation with P2 O5 but Y does not.Inconsistent enrichment processes of REYs are suggestive of complex sources of Y.Thus,seafloor hydrothermal fluids were not the direct source of Y.Normal seawater mixed with terrestrial sources might have contributed to the origin of Y here.This study could lead to improvements in Y mineral resource explorations and the situation involving the global REYs supply crisis.

Concerning the Original Viewpoint of Biogeologic Accumulation of the Old Bedded Phosphorites in the Khubsugul and Zavkhan Basins of Mongolia

This paper concerns deals with?biogeologic?accumulation and their peculiarities, lithological unites of the phosphorite-bearing formations of these basins and an evolution of the old biota. Old bedded phosphorites are believed to be connected with specific biogeological events happening in the Neoproterozoic glaciation, which was followed by rapid deglaciation,?Ediacaran bioradiation and the “great” postglacial transgression bearing phosphorites at its initial phase. The Mongolian phosphate basins give evidence of this phenomenon. Khubsugul basin is located in the northern Mongolia. The Neoproterozoic-Cambrian phosphorite-bearing khubsugul group is subdivided into 3 formations as ongolik, kheseen and erkhelnuur which are rich in organic fossils (a group of cyanobacterial mats, archaeocyaths, trilobites) in the ascending order. The Zavkhan basin lies in the western Mongolia. The Ediacaran-lower Cambrian sediments are divided into five formations: Maikhanuul (diamictites), Tsagaanolom (phosphorite-bearing carbonate), Bayangol, Salaanygol and Khairkhan. All the formations contain the paleontological fossils (algae, sponges, cyanobacterial mats, ichnocoenosis, soft-bodied fauna, archaeocyaths, etc.). Bedded phosphorites are the object for comprehensive research of bacterial paleontology. It is shown at example of the Mongolian Khubsugul and Zavkhan sea shelf phosphate basins. The expounded actual material clearly shows that the heterogeneous biologic activity, suitable geologic (transgressive systems tracts) and paleogeographic (glaciations, warm climate, etc.) conditions played an important role in the formation and accumulation of the biogenic bedded phosphorites.

Geochemical Characteristics and Occurrence States of RE Element in Phosphorite in Xinhua , Zhijin, Guizhou

The RE and composition of trace elements analysis show that phosphorite-ores are rich in ∑ RE concentration generally in Xinhua, Zhijin.The phosphorites were measured to gather LRE and HRE element.It is higher than other rocks.The phosphorite has enriched Y, La and Nd chemical element.There are leading characteristics of concentrated La, LRE and Y, HRE.The chondrite-normalized RE element patterns of the Xinhua dolomitic phosphorite distribute mode for rightwards type to one side of the curve.LRE/HRE ＞ 1, (La/Sm)N ＞ (Gd/Yb)N, and all indicate that LRE content is higher than HRE.The test mode of chemical analysis of single mineral, chemistry phase analysis, scan electric analysis and micro-electronics probe analysis were adopted.The chart of EDAX showed that there was representative element-Y(RE) in exsiting.There was no independent mineral of the RE.It is show that part of the few rare earth chemical element is adsorbed by the clay mineral, much for the type of quality isomorphic form exist in the apatite crystal structure of phosphorite inside.

Rare earth element enrichment in sedimentary phosphorites formed during the Precambrian-Cambrian transition,Southwest China

Numerous sedimentary phosphorites in Southwest China were formed around the Precambrian–Cambrian transition(PC–C),including the upper Ediacaran Doushantuo Formation and lower Cambrian Gezhongwu Formation.The Gezhongwu phosphorites in Zhijin exhibit marked rare earth element(REE)enrichment(>1000 ppm),and may represent new REE resources.Although the main characteristics of the Gezhongwu phosphorites have been well constrained,the REE enrichment mechanisms remain unclear.We undertook a comparative study of three typical sedimentary phosphorites with variable REE contents formed at the PC–C transition in central Guizhou Province,Southwest China.These include sections A and B of the Doushantuo phosphorites(560±8 Ma)from the Weng’an area(i.e.,WA-A and WA-B),and the Gezhongwu phosphorites(527±24 Ma)from the Zhijin area(ZJ).The phosphorites were investigated with state-of-the-art macroscale to nanoscale analytical techniques.In contrast to the extraordinary REE enrichment in the ZJ phosphorites(average RREE=1157 ppm),the phosphorites in WA-A(average RREE=234 ppm)and WA-B(average RREE=114 ppm)are REE-poor.Elemental mapping by laser ablation–inductively coupled plasma–mass spectrometry,along with transmission electron microscopy analyses,showed the REEs in the studied phosphorites are hosted in nanoscale francolites.The 87Sr/86Sr and Y/Ho ratios of the francolite grains indicate that greater terrigenous input may have led to more REE enrichment in the WA-A than WA-B phosphorites,but this cannot explain the extraordinary REE enrichment in the ZJ phosphorites.The F/P_(2)O_(5)values of the francolite grains in the ZJ phosphorites(~0.097)are higher than those in the WA-A(~0.084)and WA-B(~0.084)phosphorites,and the grain size of the francolite in the ZJ phosphorites(~89.9 nm)is larger than those in the WA-A(~56.6 nm)and WA-B(~57.4 nm)phosphorites,indicative of more intense reworking of the ZJ than WA phosphorites during early diagenesis.A plot of Nd concentration versus Ce/Ce^(*)reveals that lower sedimentation rates characterized the ZJ phosphorites.Therefore,intense sedimentary reworking during early diagenesis resulted in more REEs being sequestered by the marine phosphates from seawater and pore waters at a lower sedimentation rate,which resulted in the extraordinary REE enrichment in the ZJ phosphorites.Our findings highlight the multiple factors that controlled formation of sedimentary phosphorites around the PC–C transition(especially the intense reworking and redox conditions of the overlying seawater),and provide further insights into REE enrichment in sedimentary phosphorites worldwide.

Sulfur and Oxygen Isotopes of Sulfate Extracted from Early Cambrian Phosphorite Nodules： Implications for Marine Redox Evolution in the Yangtze Platform

Phosphorite nodule beds are discovered in the black shale of basal Niutitang Formation throughout the Yangtze Platform in South China, recording an important phosphorite-generation event. Platform-wide phosphorite precipitation requires special oceanographic and geochemical conditions, thus the origin of the Niutitang phosphorite nodules may provide valuable information about the ocean chemistry in the Early Cambrian. In this study, we measured sulfur and oxygen isotopic compositions of sulfate extracted from phosphorite nodules collected from the basal Niutitang Formation. Phosphorite associated sulfate（PAS） is a trace amount of sulfate that incorporates into crystal lattice during phosphorite precipitation, accordingly PAS records the geochemical signals during phosphorite nodule formation. Sulfur isotopic composition of PAS（δ^（34）S_（PAS）） ranges from-1.16‰ to ＋24.48‰（mean=＋8.19‰, n=11）, and oxygen isotopic value（δ^（18）O_（PAS）） varies between-5.3‰ and ＋26.3‰（mean=＋7.0‰, n=8）. Most phosphorite nodules have low δ^（34）SPAS and low δ^（18）O_（PAS） values, suggesting PAS mainly derived from anaerobic oxidation of H_2S within suboxic sediment porewater. We propose that phosphate was delivered to the Yangtze Platform by a series of upwelling events, and was scavenged from seawater with the precipitation of FeOOH. The absorbed phosphate was released into suboxic porewater by the reduction of FeOOH at the oxic-suboxic redox boundary in sediments, and phosphorite nodule precipitated by the reaction of phosphate with Ca^（2＋） diffused from the overlying seawater. The platform-wide deposition of phosphorite nodules in the basal Niutitang Formation implies the bottom water might be suboxic or even oxic, at least sporadically, in Early Cambrian. We speculate that the intensified ocean circulation as evident with frequent occurrences of upwelling events might be the primary reason for the episodic oxidation of the Yangtze Platform in Early Cambrian.

Rare earth element geochemistry of Cambrian phosphorites from the Yangtze Region

Analysis on P205 and REE （rare earth elements） in basal Cambrian phosphorites from the Yangtze Region, showed that the phosphorites from Bailongtan in Yunnan Province, Zhijin, Jinsha, Xishui, Zunyi, Tianzhu and Tongren in Guizhou Province, Shan- grao in Jiangxi Province, Jiangshan in Zhejiang Province and Nanjing in Jiangsu Province contained high REE contents in phos- phorites, especially those from Tianzhu and Tongren in Guizhou Province, Shangrao in Jiangxi Province, Jiangshan in Zhejiang Province and Nanjing in Jiangsu Province. Among them, the highest REE contents reached up to 1361.59×10^-6 and P205 contents up to 29.45%. In contrast, phosphorites from Kaiyang, Qingzhen and Zhenyuan in Guizhou Province had relatively low total REE con- tents and low P205 contents, with the lowest total REE content of 53.19× 10^-6, and the lowest P205 content of 0.07%. REE contents exhibited a positive correlation with phosphorous contents, indicating a close genetic relationship between REE and phosphorous ele- ment. The main reason was the difference of the sedimentary environments and the contents of phosphorous and REE in deep water mass formed in upwelling currents, at an upper slope facies （Slu） in reducing condition due to relatively closed sedimentary environ- ment. It was very difficult for the upswelling phosphorous and REE to deposit, massive phosphorous deposits were hard to be formed. At a deep water ramp facies （DRa） in the ascending process of currents, phosphorus and REE underwent differentiation rather than sedimentation. Consequently, the contents of P205 sediments and REE were low. At a shallow water ramp facies （including shoals and tidal flats） （SRa）, with active seawater circulation and phosphatic supplement, sunny weather, high nutrition and rapid growth of algae, were benefitial for the physical enrichment of carbonate sediments. Therefore, massive phosphorite deposits were easy to be tbrmed with abundant REE minerals, and finally turned into high REE beating phosphorous deposits.

New observations on spicule-like structures from Dou-shantuo phosphorites at Weng'an,Guizhou Province

Doushantuo phosphorites at Weng’an, Guizhou Province, provide a unique opportunity for the study of early evolution of multicellular organisms, including metazoans. Our light microscope and SEM observations, however, do not substantiate a sponge spicule interpretation of spicular structures. No convincing axial canals have been seen in the observed spicule population. Instead, the coexistence of some monaxonal spicules with clearly diagenetic crystal fascicles and dumbbells suggest that these monaxons may also be diagenetic in origin. Our preliminary EDS analyses detect no significant silicon in spicule-containing intraclasts (including abiotic clasts and fragments of sphaeromorphic acritarchs and algal thalli), that contain abundant monaxonal spicular structures. We, therefore, believe that the evidence for a sponge spicule interpretation of the Doushantuo spicular structures are at best ambiguous at present; these alleged sponge spicules are indistinguishable from coexistent diagenetic crystals.

Marine Redox Conditions in the Early Cambrian Ocean: Insights from the Lower Cambrian Phosphorite Deposits, South China

It is generally considered that a significant change in oceanic redox conditions occurred during the Ediacaran-Cambrian transition. However, there are currently two major conflicting views on the degree of oxygenation of deep water（oxic vs. ferruginous） during this interval. To date, the oxygenation conditions of the Early Cambrian ocean have not been well constrained. The oxygenation magnitude and mechanism of the Early Cambrian ocean could be critical to the significant biological evolution of the ＂Cambrian Explosion＂. To constrain the Early Cambrian oceanic redox environment, we conducted an integrated study on iron and sulfur isotopes and redox-sensitive elements（Mo, U, and V） of Lower Cambrian phosphorite deposits from two shallow sections（Meishucun and Gezhongwu） and a deeper water section（Zunyi） from the Yangtze Platform, South China. The near zero δ^（56）Fe values from the two shallow sections studied here reflect oxic conditions in the lower phosphorite deposition. An obvious positive shift in δ^（56）Fe and redox-sensitive element content was observed in the middle parts of the two shallow water sections, which might reflect loss of light iron by dissimilatory iron reduction during early diagenesis under suboxic shallow water in the platform. However, the highly positive δ^（56）Fe values in the deep section could reflect a lower oxidation degree of dissolved Fe（II） under anoxic deep water. The data suggest redox-stratified oceanic conditions during the Early Cambrian, in which completely oxygenated shallow water（platform） coexisted with anoxic deep water（slope）. We propose that prolonged upwelling of dissolved organic carbon（DOC）-, Fe（II）- and phosphorus-rich anoxic deep water in a redox-stratified ocean could have increased exchange with the open ocean, resulting in major phosphorite deposition in oxic-suboxic conditions. The progressive oxygenation of the ocean may have facilitated the Early Cambrian biotic diversification.

Separation and recovery of associated rare earths from the Zhijin phosphorite using hydrochloric acid

The separation and extraction of associated rare earths from the Zhijin phosphorite mine is of great interest. Based on previous studies, the hydrolysis of phosphate ore using hydrochloric acid was systematically studied through extensive testing. Experiments were conducted to separate and recover the rare earths from the hydrolysis solution. Kinetic studies on the acidolysis of phosphorite using hydrochloric acid show that the use of hydrochloric acid in the acidolysis of phosphorite is mainly controlled by a chemical reaction and is also a diffusion-controlled reaction. When 210 L of HCL per 100 kg of phosphorite was used at 30 ℃ for 360 min, 96.1% of the P_2 O_5 and 95.0% of the rare earths are leached from the phosphorite. After defluorination and purification, the pH of the phosphate-acid solution is adjusted to 2.1 using sodium hydroxide, and a rare earth concentrate with rare earth content of 1.76 wt%is obtained; i.e., 90.1% of the rare earths are recovered. The rare earth content is increased to more than5 wt% through multiple enrichment processes, with a total yield of 59.5%.

Leaching isomorphism rare earths from phosphorite ore by sulfuric acid and phosphoric acid

Most of the phosphorite deposits in the world contain isomorphism rare earths （RE） which are considerably difficult to be leached into solution in the wet phos- phoric acid process. In this work, a systematic study of leaching RE using sulfuric acid, phosphoric acid, mixed acid and two-step leaching of phosphoric acid and sulfuric acid was performed. The aims are to illuminate the main factors that inhibit RE leaching and to provide insights into the further enrichment of RE in the wet phosphoric acid solution. The results indicate that H2SO4 is not an effective acid for leaching isomorphism RE from phosphorite ore. The low RE leaching efficiency attributes to the RE cocrystallized and encapsulated by phosphogypsum （PG） as well as the precipitation of RE by RE sulfates or phosphates. High concentration of H3PO4 can enhance the dissolution and diffusion of RE ions. Hence, the optimized leaching mode of improving RE leaching efficiency is to adequately dissolve phosphorite ores in high concentration of H3PO4 solution and then add H2SO4 to crystallize PG. The effect of corystallization or encapsulation of PG on RE can be decreased due to the crystallizing mode of PG in the bulk solution instead of on the interface of solid reactants. RE leaching efficiency can be high up to 65% by the optimized leaching mode.

Rare earth element(REE) geochemistry of phosphorites of the Sonrai area of Paleoproterozoic Bijawar basin,Uttar Pradesh,India

The rare earth element（REE） data from the Paleoproterozoic Bijawar basin,Sonrai phosphorites were used to interpret the depositional conditions of the phosphorites.The post archean Australian shales（PAAS） normalized REE patterns of the Sonrai phosphorites were characterized by negative Ce and positive Eu anomalies.Middle rare earth elements（MREE）-enrichment was a characteristic feature.Phosphorites showing the diagenetic effects on the REE patterns were limited.The observed Eu anomaly was indicative of an anoxic（or sulphate reducing） diagenetic environment of phosphate formation.Mixing of sea water and upwelling during the Paleoproterozoic was responsible for the recording of positive Eu and negative Ce anomalies in the Sonrai phosphorites.

Hydrothermal sedimentaion of Wengfu phosphorite deposit

THE Wengfu phosphorite deposit, a superlarge ore deposit, is located in the counties of Weng an andFuquan, Central Guizhou, China. The deposit has been considered as typical sedimentary one since itwas found, but our new approach suggests that its formation be related to contemporaneous submarine hydrothermal activity. The Wengfu phospohorite deposit, belonging to Doushantuo stage of Late Sinian （Latest Precambrian）, was divided into two ore layers intercalated by dolomites and siliceous rocks. In the phosphoritesthere exist abundant fossils, including newly found "Weng an Biota" which contain the fossils of multicellular thallophytes as well as animal embryos and sponges. Besides the common sedimentary structures, the phosphorites and the coexisting siliceous rocks alsopossess obvious hydrothermal sedimentation features, which are presented as the following: （i） The coexisting cherts are, lenticular in distribution and with high SiO2 purity and high homogeneous temperatures （up to 150℃） of the inclusions, characterized by hydrothermal sedimentation. （ii） The special "pellets" or "pisolites" formed by hydrothermal eruption are common in the phos-

Sulfur isotope and its significance of the Late Sinian phosphorites in Kaiyang District, Guizhou Province

Accepting presence of sulfate (SO42-) in francolite lattice as an isomorphous substitution for phosphate (PO43-), Nathan and Nielsen and Benmore et al. investigated sulfur isotopes of the sulfate within francolite for the marine phosphorites formed since the Permian, and origin, sedimentary and diagenetic environments of phosphorites. Here,

A Five-stage Evolution of Earth's Phosphorus Cycle

Phosphorus(P)is a key biological nutrient and probably the ultimate limiter of marine productivity during Earth history.In recent years,a wealth of new knowledge has revolutionized our understanding of the global P cycle,yet its longterm evolution remains incompletely documented.In this paper,we review the effects of three major controlling factors on the long-term evolution of the global P cycle,i.e.,tectonics,marine redox conditions,and bio-evolution,on the basis of which a five-stage model is proposed:StageⅠ(>~2.4 Ga),tectonic-lithogenic-controlled P cycling;StageⅡ(~2.4 Ga to 635Ma),low-efficiency biotic P cycling;StageⅢ(~635 Ma to 380 Ma),transitional biotic P cycling;StageⅣ(~380 Ma to near-modern),high-efficiency biotic P cycling;and Stage V(Anthropocene),human-influenced P cycling.This model implies that the earlier-proposed Ediacaran reorganization of the marine P cycle may represent only the start of a-250-Myr-long transition of the Earth's P cycle(StageⅢ)between the low-efficiency biotic mode of the Proterozoic(StageⅡ)and the high-efficiency biotic mode of the Phanerozoic(StageⅣ).The development of biologically-driven,high-efficiency P cycling may have been a key factor for the increasing frequency and volume of phosphorite deposits since the late Neoproterozoic.

Main Patterns of Geochemistry of Phosphorus

The paper presents the main conclusions of the Russian monograph “Geochemistry of Phosphorus” (2020). Based on statistical processing of ~6100 sample averages (from ~190,000 analyses), new estimations of World averages (Clarke values) for Р2O5, % (and P, %), phosphorus-titanium module (P2О5/TiO2), phosphorus-calcium module (P2O5/CaO), phosphorus-iron module (P2О5/Fe2O3), and phosphorus-total iron module (P2O5/Fe2O3 + FeO). Many estimates have been made for the first time. In addition to the new Clarke estimates, sometimes very different from previous ones, the work carried out has led to a number of new conclusions. In particular, the titanium geochemical barrier for phosphorus has been first estimated, all the 11 genotypes of phosphogenesis have been named and characterized, five genetic correlations of phosphogenesis have been described, lithochemistry methods have been successfully applied to characterize the phosphorites. Due to the large breadth of generalization, the monograph has a large theoretical and applied value.