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 ...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.展开更多
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 c...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.展开更多
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 e...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.展开更多
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...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.展开更多
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 phosphor...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.展开更多
The authors investigated the effect of Bacillus mucilaginosus on weathering of phosphorite. Analysis of different proteins was of significance in exploring the molecular biological mechanism in the bacterial weatherin...The authors investigated the effect of Bacillus mucilaginosus on weathering of phosphorite. Analysis of different proteins was of significance in exploring the molecular biological mechanism in the bacterial weathering process. The concrete methods are described as follows: Mineral powder was put into liquid culture medium and B. mucilaginosus was incubated in the medium. The control (group) had no mineral powder in the medium. The treatments and controls were cultured simultaneously under the same condition. In a few days, the supernatant was filtrated, the main cations (Ca2+, Mg2+, Na+, Mn2+, Al3+, Fe3+, K+) were measured by ICP-OES, and the contents of water soluble phosphorus (Pws) and silicon (Siws) were determined by colorimetry. The residual solid was weighed on the filter paper, followed by digestion with concentrated HNO3. The concentrations of the main cations and Pws, Siws in the digest liquid were measured by using the method mentioned above. After the supernatant was centrifuged, the precipitation was used to analyze the protein differences between the treatment groups and the control groups by 2-dimentional gel electrophoresis (2-DE). The experimental results showed that apatite and quartz were partially weathered, but kaolinite was dissolved completely. The population of bacteria increased when mineral powder was added in the liquid medium. Software analysis and comparison of the 2-DE pictures of bacterial proteins revealed 1134 visible protein spots in the treatment group, and 729 visible protein spots in the control group. To compare the bacterial protein expression contents of the treatment group with those of the control group, there were 496 different protein spots, including 214 protein spots which indicated that the protein contents increased, 75 protein spots were indicative of a decrease, and 207 proteins were newly synthesized. It is proposed that the increased bacterial contents may be related to some protein expression and activation after the input of mineral powder. Newly synthesized proteins, the increase of expression contents and the reduction of proteins may be connected with bacterial metabolic regulations, cell activation and signal transmission.展开更多
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...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.展开更多
The Cambrian Gezhongwu Formation in Southwest China is the lowest Cambrian phosphorite unit. The Formation belongs to the Meishucun stage with small shelly fossils. Rare-earth element (REE) data from the Gezhongwu pho...The Cambrian Gezhongwu Formation in Southwest China is the lowest Cambrian phosphorite unit. The Formation belongs to the Meishucun stage with small shelly fossils. Rare-earth element (REE) data from the Gezhongwu phosphorites of Zhijin documented the depositional conditions. The total REE concentrations are high in the Gezhongwu phosphorites, which are especially rich in yttrium. The PAAS-normalized REE patterns of the Gezhongwu phosphorites are characterized by negative Ce anomalies and slight enrichment of MREE, as being hat-shaped. The hat-shaped patterns suggest that the REE originated from depositional environments rather than from subsequent diagenesis. The negative Ce anomalies indicate that the depositional environments are oxic. The positive Eu anomaly, the high total REE and the hat-shaped REE pattern revealed contributions from the normal marine environment mixed with hydrothermal water to the REE budget of the Gezhongwu phosphorites.展开更多
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...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.展开更多
Egyptian phosphorites from Abu Tartur (Western Desert), El Mahamide mine (Nile Valley) and Rabah mine (Eastern Desert) show variable degrees of relative REE enrichment. Black plateau phosphorites of Abu Tartur are sub...Egyptian phosphorites from Abu Tartur (Western Desert), El Mahamide mine (Nile Valley) and Rabah mine (Eastern Desert) show variable degrees of relative REE enrichment. Black plateau phosphorites of Abu Tartur are substantially enriched in REE as compared to the Red Sea and Nile Valley phosphorites. P-rich organic matter from the Abu Tartur and Rabah mines recorded negative Ce and positive Eu anomalies. Positive Eu anomaly reveals an anoxic event prior to the phase of Late Cretaceous phosphate formation. Ce is a redox indicator. Mixing of sea water and upwelling during the Late Cretaceous was responsible for the recording of positive Eu and negative Ce anomalies in the Egyptian phosphorites.展开更多
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 o...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.展开更多
Geochemical characteristics of scandium are described with respect to its source, evolution and correlation with REE as observed in Late Sinian and Early Cambrian phosphorites and tuffs in Guizhou. Comparison of chond...Geochemical characteristics of scandium are described with respect to its source, evolution and correlation with REE as observed in Late Sinian and Early Cambrian phosphorites and tuffs in Guizhou. Comparison of chondrite\|normalized REE patterns and some other parameters between the phosphorite and tuff shows that scandium and REE are most likely to have been derived from earlier or contemporaneous marine volcanics or tuffs, with no indication of genetic link to the purple shales, siltstones and dolomites in the area. The conditions under which the Sc bearing phosphorites were formed are discussed in the light of sulfur isotopes and Eh Ph constrains.展开更多
The Campanian\|Maastrichtian phosphatic deposits in Egypt, called the Duwi Formation, comprise a part of the extensive Middle East to North African phosphogenic province of Late Cretaceous to Paleogene age. The provin...The Campanian\|Maastrichtian phosphatic deposits in Egypt, called the Duwi Formation, comprise a part of the extensive Middle East to North African phosphogenic province of Late Cretaceous to Paleogene age. The province holds the greatest accumulation of phosphorites in the geological history, possibly in excess of 70 billion metric tons. The phosphate resources in Egypt alone exceed 3 billion metric tons. Two\|third of these three billions occur only in the Abu\|Tartur area.\; Among the phosphorite deposits in Egypt, the phosphorites of the Abu\|Tartur area are characterized by high contents of iron ranging from 3% to 7% with an average of 5%. The detailed mineralogical and geochemical studies on the Abu\|Tartur phosphorites revealed that iron is found in the form of pyrite, ankerite, clay minerals, microinclusions, and iron oxide. Pyrite, which is the major fraction, occurs as filling cement and partial to complete replacement of phosphatic grains and confined to the fresh phosphorites while iron oxide occurs as cryptocrystalline aggregates of red to brown particles and is confined to the weathered outcrops. Exclusive relations between pyrite in the fresh phosphorite samples inside the Abu\|Tartur mine and iron oxide in the equivalent horizon of the weathered exposure indicated that iron oxide was formed by the oxidation of pyrite as a result of weathering. All of these forms harm the quality of ore, manufacturing processes, and the produced phosphoric acid and fertilizers.展开更多
稀土元素和钇(REY)是极其重要的战略资源,被誉为“工业维生素”(蒋训雄等,2011),随着科技的进步和应用技术的不断突破,稀土氧化物的价值越来越大,全球市场对稀土(尤其是重稀土)的需求量与日俱增。我国是世界上稀土资源最丰富的国家,白...稀土元素和钇(REY)是极其重要的战略资源,被誉为“工业维生素”(蒋训雄等,2011),随着科技的进步和应用技术的不断突破,稀土氧化物的价值越来越大,全球市场对稀土(尤其是重稀土)的需求量与日俱增。我国是世界上稀土资源最丰富的国家,白云鄂博稀土矿床和华南离子吸附粘土型矿床提供了世界REY产量的95%以上(Emsbo et al.,2015)。展开更多
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 Gezhong...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.展开更多
基金Project supported by the National Natural Science Foundation of China (40372047, 50164001)
文摘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.
文摘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.
基金the Natural Science Foundation of Guizhou Province (QianKeHe J[2005]2098)
文摘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.
文摘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.
基金supported by the United Foundation of National Natural Science Foundation of China(Grant Numbers:41972095,U181240004,9206220039)the Public Beneficial,Basic Geological Project of Department of Land and Resources of Guizhou Province(Grant Number:2016-09-1).
文摘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.
基金the financial support from the Ministry of Science and Technology of China(Grant No.2006CB403200)the Knowledge Innovation Program of the Chinese Academy of Sciences(No.KZCX3-SW-140)the National Natural Science Foundation of China(Grant No.40773069).
文摘The authors investigated the effect of Bacillus mucilaginosus on weathering of phosphorite. Analysis of different proteins was of significance in exploring the molecular biological mechanism in the bacterial weathering process. The concrete methods are described as follows: Mineral powder was put into liquid culture medium and B. mucilaginosus was incubated in the medium. The control (group) had no mineral powder in the medium. The treatments and controls were cultured simultaneously under the same condition. In a few days, the supernatant was filtrated, the main cations (Ca2+, Mg2+, Na+, Mn2+, Al3+, Fe3+, K+) were measured by ICP-OES, and the contents of water soluble phosphorus (Pws) and silicon (Siws) were determined by colorimetry. The residual solid was weighed on the filter paper, followed by digestion with concentrated HNO3. The concentrations of the main cations and Pws, Siws in the digest liquid were measured by using the method mentioned above. After the supernatant was centrifuged, the precipitation was used to analyze the protein differences between the treatment groups and the control groups by 2-dimentional gel electrophoresis (2-DE). The experimental results showed that apatite and quartz were partially weathered, but kaolinite was dissolved completely. The population of bacteria increased when mineral powder was added in the liquid medium. Software analysis and comparison of the 2-DE pictures of bacterial proteins revealed 1134 visible protein spots in the treatment group, and 729 visible protein spots in the control group. To compare the bacterial protein expression contents of the treatment group with those of the control group, there were 496 different protein spots, including 214 protein spots which indicated that the protein contents increased, 75 protein spots were indicative of a decrease, and 207 proteins were newly synthesized. It is proposed that the increased bacterial contents may be related to some protein expression and activation after the input of mineral powder. Newly synthesized proteins, the increase of expression contents and the reduction of proteins may be connected with bacterial metabolic regulations, cell activation and signal transmission.
基金supported by the National Natural Science Foundation of China (No. U1812402)the Public Beneficial and Basic Geological Project from the Department of Land and Resources of Guizhou Province (No. 2016-09-1)。
文摘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.
文摘The Cambrian Gezhongwu Formation in Southwest China is the lowest Cambrian phosphorite unit. The Formation belongs to the Meishucun stage with small shelly fossils. Rare-earth element (REE) data from the Gezhongwu phosphorites of Zhijin documented the depositional conditions. The total REE concentrations are high in the Gezhongwu phosphorites, which are especially rich in yttrium. The PAAS-normalized REE patterns of the Gezhongwu phosphorites are characterized by negative Ce anomalies and slight enrichment of MREE, as being hat-shaped. The hat-shaped patterns suggest that the REE originated from depositional environments rather than from subsequent diagenesis. The negative Ce anomalies indicate that the depositional environments are oxic. The positive Eu anomaly, the high total REE and the hat-shaped REE pattern revealed contributions from the normal marine environment mixed with hydrothermal water to the REE budget of the Gezhongwu phosphorites.
文摘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.
文摘Egyptian phosphorites from Abu Tartur (Western Desert), El Mahamide mine (Nile Valley) and Rabah mine (Eastern Desert) show variable degrees of relative REE enrichment. Black plateau phosphorites of Abu Tartur are substantially enriched in REE as compared to the Red Sea and Nile Valley phosphorites. P-rich organic matter from the Abu Tartur and Rabah mines recorded negative Ce and positive Eu anomalies. Positive Eu anomaly reveals an anoxic event prior to the phase of Late Cretaceous phosphate formation. Ce is a redox indicator. Mixing of sea water and upwelling during the Late Cretaceous was responsible for the recording of positive Eu and negative Ce anomalies in the Egyptian phosphorites.
基金Projbect supported by the National Natural Science Foundation of China(50164001 )
文摘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.
文摘Geochemical characteristics of scandium are described with respect to its source, evolution and correlation with REE as observed in Late Sinian and Early Cambrian phosphorites and tuffs in Guizhou. Comparison of chondrite\|normalized REE patterns and some other parameters between the phosphorite and tuff shows that scandium and REE are most likely to have been derived from earlier or contemporaneous marine volcanics or tuffs, with no indication of genetic link to the purple shales, siltstones and dolomites in the area. The conditions under which the Sc bearing phosphorites were formed are discussed in the light of sulfur isotopes and Eh Ph constrains.
文摘The Campanian\|Maastrichtian phosphatic deposits in Egypt, called the Duwi Formation, comprise a part of the extensive Middle East to North African phosphogenic province of Late Cretaceous to Paleogene age. The province holds the greatest accumulation of phosphorites in the geological history, possibly in excess of 70 billion metric tons. The phosphate resources in Egypt alone exceed 3 billion metric tons. Two\|third of these three billions occur only in the Abu\|Tartur area.\; Among the phosphorite deposits in Egypt, the phosphorites of the Abu\|Tartur area are characterized by high contents of iron ranging from 3% to 7% with an average of 5%. The detailed mineralogical and geochemical studies on the Abu\|Tartur phosphorites revealed that iron is found in the form of pyrite, ankerite, clay minerals, microinclusions, and iron oxide. Pyrite, which is the major fraction, occurs as filling cement and partial to complete replacement of phosphatic grains and confined to the fresh phosphorites while iron oxide occurs as cryptocrystalline aggregates of red to brown particles and is confined to the weathered outcrops. Exclusive relations between pyrite in the fresh phosphorite samples inside the Abu\|Tartur mine and iron oxide in the equivalent horizon of the weathered exposure indicated that iron oxide was formed by the oxidation of pyrite as a result of weathering. All of these forms harm the quality of ore, manufacturing processes, and the produced phosphoric acid and fertilizers.
文摘稀土元素和钇(REY)是极其重要的战略资源,被誉为“工业维生素”(蒋训雄等,2011),随着科技的进步和应用技术的不断突破,稀土氧化物的价值越来越大,全球市场对稀土(尤其是重稀土)的需求量与日俱增。我国是世界上稀土资源最丰富的国家,白云鄂博稀土矿床和华南离子吸附粘土型矿床提供了世界REY产量的95%以上(Emsbo et al.,2015)。
基金This work was financially supported by the National Natural Science Foundation of China(Grant Nos.41825003,41921003)Key Research Program of the Institute of Geology&Geophysics,CAS(Grant No.IGGCAS-201901)+2 种基金Guangdong Special Support Program(Grant No.2019TX05L169)Science and Technology Planning Project of Guangdong Province,China(Grant No.2023B1212060048)Youth Innovation Promotion Association CAS(Grant No.2021353).
文摘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.