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The present study aims to elucidate the possible sources of uranium and thorium content in the Campanian–Maastrichtian phosphorites from the Duwi Formation in the Nile Valley and Red Sea by conducting facies analysis and sequential leaching method. Nile Valley samples were collected from the El-Sibaiya East area, while those of the Red Sea were collected from two locations: Hamadat and Zug El Bahar. The petrographic investigation revealed that the Sibaiya East phosphorites exhibit peloidal bioclastic phospharenite–phospharudite microfacies, while Hamadat and Zug El Bahar phosphorites display peloidal bioclastic phosphalutite and silicified peloidal bioclastic phospharenite microfacies, respectively. Besides, U–Th bearing accessory minerals, such as zircon and monazite occur in Sibaiya East phosphorites. Thorium is present in Zug El Bahar phosphorites as minute accumulations associating apatite and quartz. Moreover, uranium is found with vanadium and iron as fine patches in the Sibaiya East phosphorite, and as small disseminations associated with Ca and Si in the Hamadat phosphorite. The X-ray diffraction shows that the investigated phosphorites are essentially built up of hydroxyl apatite Ca 5 (PO 4 ) 3 (OH) and quartz SiO 2. To accurately evaluate the bioavailability and mobility of uranium and thorium in the investigated phosphorites, it was necessary to identify the overall concentration and the various chemical forms of these elements by a five-step sequential leaching technique. The results indicate that Th and U are more abundant in the Red Sea phosphorites than in the Nile Valley phosphorites. Furthermore, Th is not bio-available and it is mostly found in the residue as Th-bearing minerals. Uranium, unlike Th is bio-available and fractionates among all fractions, indicating that U accumulation is the result of various diagenetic processes.

Water plays a critical role in securing the mine production and domestic consumption in mining areas. This research was carried out to assess the water quality status and to identify the hydrochemical processes contributing to the dissolved constituents of the water in the Guohua phosphorite mine, Guizhou Province, China. Multivariate statistical techniques and correlation analysis were employed to gain a better understanding of the hydrogeochemical processes, and water quality for domestic and irrigation purposes was also assessed. The results indicate that groundwater and surface water quality in the phosphorite mine area is currently excellent with low concentrations of major ions, salinity, and trace metals. Whereas, E. coli is excessive in groundwater and surface water, and treatment is required before the water is used for drinking purpose. Groundwater and surface water are, however, suitable for agricultural purposes. The major ions are Ca 2+ , Mg 2+ , and HCO 3 − , and all water samples are predominantly of the HCO 3 –Ca·Mg type. Hierarchical cluster analysis (HCA) indicates that the water chemistry in the mining area is regulated by natural processes that are controlled by the different geological formations and different hydrogeological settings. Carbonate dissolution/precipitation is the key factor controlling the concentrations of Ca 2+ , Mg 2+ , and HCO 3 – . Pyrite oxidation is an important factor influencing the concentration of SO 4 2– , whereas evaporation is a minor factor regulating the water chemistry in the mining area. The study results are beneficial for sustainable water quality management in the mining area, and they will also interest mine hydrogeologists and practitioners of the world as a reference for relevant studies in other regions.

Currently, there is an increasing industrial demand for rare earth elements (REE) as these elements are now integral to the manufacture of many carbon-neutral technologies. The depleting REE ores and increasing mining costs are prompting us to consider alternative sources for these valuable metals, particularly from waste streams. Although REE concentrations in most of the alternative resources are lower than current REE ores, some sources including marine sediments, coal ash, and industrial wastes, such as red mud, are emerging as promising with significant concentrations of REE. This review focuses on the alternative resources for REE, such as ocean bottom sediments, continental shelf sediments, river sediments, stream sediments, lake sediments, phosphorite deposits, industrial waste products, such as red mud and phosphogypsum, coal, coal fly ash and related materials, waste rock sources from old and closed mines, acid mine drainage, and recycling of e-waste. Possible future Moon exploration and mining for REE and other valuable minerals are also discussed. It is evident that REE extractions from both primary and secondary ores alone are not adequate to meet the current demand, and sustainable REE recovery from the alternative resources described here is also necessary to meet the growing REE demand. An attempt is made to identify the potential of these alternative resources and sustainability challenges, benefits, and possible environmental hazards to meet the growing challenges of reaching the future REE requirements.

Phosphorite-type rare earth deposits, which are one of the important types of rare earth elements (REE) ore deposits, have attracted increasing attention because of the extreme enrichments in heavy rare earth elements (HREE), including Yttrium (Y). In this study, in situ geochemical analyses of apatite grains from Zhijin phosphorites were conducted using electron probe microanalysis (EMPA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Based on EPMA mapping analysis, we show that rare earth elements and Yttrium (REY) entering into the crystal lattice by isomorphism rather than by inclusions of REY-bearing accessory minerals. The post-Archean Australian Shales (PAAS)-normalized REY patterns of the apatite grains are characterized by hat-shaped MREE-enriched patterns. We interpret that this pattern may reflect the REE distribution of seawater at that time. We propose that in a local, reducing environment, dramatically increased the concentration of REY in seawater, and resulted in the MREE-enriched patterns in the ancient ocean. The main mechanism for the genesis of the Zhijin phosphorite deposit is the apatite crystallizes during the mixing process of REY- and P-rich fluid and oxidizing seawater.

Siderophores are extra-cellular inducible compounds produced by aerobic microorganisms and plants to overcome iron insolubility via its chelation and then uptake inside the cell. This work aims to study the characteristics of siderophore that is produced by a rhizosphere-inhabiting fungus. This fungus has been morphologically and molecularly identified as Aspergillus niger with the ability to produce 87% siderophore units. The obtained siderophore in PDB medium gave a positive result with tetrazolium test and a characteristic spectrum with a maximum absorbance at 450 nm in FeCl3 test that did not shift in response to different pH degrees (5–9). This indicates that the obtained siderophore is a trihydroxymate in nature. After purification, the FTIR and NMR analyses showed that the obtained siderophore is considered to be ferrichrome. The purified siderophore has been further evaluated as a tool to extract uranium, thorium and rare earth elements (REEs) from Egyptian phosphorites obtained from Abu Tartur Mine area. The inductively coupled plasma atomic emission spectroscopy analysis showed that the highest removal efficiency percentage was for uranium (69.5%), followed by samarium (66.7%), thorium (55%), lanthanum (51%), and cerium (50.1%). This result confirmed the ability of hydroxymate siderophores to chelate the aforementioned precious elements, a result that paves the way for bioleaching to replace abiotic techniques in order to save the cost of such elements in an environmentally friendly way.Graphic abstract

Marine phosphorites are known to concentrate rare earth elements and yttrium (REY) during early diagenetic formation. Much of the REY data available are decades old and incomplete, and there has not been a systematic study of REY distributions in marine phosphorite deposits that formed over a range of oceanic environments. Consequently, we initiated this study to determine if marine phosphorite deposits found in the global ocean host REY concentrations of high enough grade to be of economic interest. This paper addresses continental-margin (CM) and open-ocean seamount phosphorites. All 75 samples analyzed are composed predominantly of carbonate fluorapatite and minor detrital and authigenic minerals. CM phosphorites have low total REY contents (mean 161 ppm) and high heavy REY (HREY) complements (mean 49%), while seamount phosphorites have 4–6 times higher individual REY contents (except for Ce, which is subequal; mean ΣREY 727 ppm), and very high HREY complements (mean 60%). The predominant causes of higher concentrations and larger HREY complements in seamount phosphorites compared to CM phosphorites are age, changes in seawater REY concentrations over time, water depth of formation, changes in pH and complexing ligands, and differences in organic carbon content in the depositional environments. Potential ore deposits with high HREY complements, like the marine phosphorites analyzed here, could help supply the HREY needed for high-tech and green-tech applications without creating an oversupply of the LREY.

The Nile Valley is a main area for Egyptian phosphorites. The studied samples from the eastern and western sides of the Nile Valley showed similarities in their characteristics, suggesting one depositional basin, but they varied in their uranium content, with averages recorded at 91.7 and 44.83 ppm on the eastern and western sides, respectively. The evidence pointed out that initially the uranium was formed by adsorption onto the iron oxides and organic matter surfaces, then it was partially removed under the effect of groundwater, and the removal was deeper in the western phosphorites than the eastern ones.

A review of the compositional features of Tunisia, Algeria, and Morocco phosphorites is proposed in order to assess and compare the paleoenvironmental conditions that promoted the deposit formation as well as provide information about their economic perspective in light of growing worldwide demand. Since these deposits share a very similar chemical and mineralogical composition, the attention was focused on the geochemistry of rare earth elements (REEs) and mostly on ΣREEs, Ce and Eu anomalies, and (La/Yb) and (La/Gd) normalized ratios. The REEs distributions reveal several differences between deposits from different locations, suggesting mostly that the Tunisian and Algerian phosphorites probably were part of the same depositional system. There, sub-reducing to sub-oxic conditions and a major REEs adsorption by early diagenesis were recorded. Conversely, in the Moroccan basins, sub-oxic to oxic environments and a minor diagenetic alteration occurred, which was likely due to a different seawater supply. Moreover, the drastic environmental changes associated to the Paleocene–Eocene Thermal Maximum event probably influenced the composition of Northern African phosphorites that accumulated the highest REEs amounts during that span of time. Based on the REEs concentrations, and considering the outlook coefficient of REE composition (Koutl) and the percentage of critical elements in ΣREEs (REEdef), the studied deposits can be considered as promising to highly promising REE ores and could represent a profitable alternative source for critical REEs.

The Ediacaran Period (635 to 541 Ma) marks the global transition to a more productive biosphere, evidenced by increased availability of food and oxidants, the appearance of macroscopic animals, significant populations of eukaryotic phytoplankton, and the onset of massive phosphorite deposition. We propose this entire suite of changes results from an increase in the size of the deep-water marine phosphorus reservoir, associated with rising sulfate concentrations and increased remineralization of organic P by sulfate-reducing bacteria. Simple mass balance calculations, constrained by modern anoxic basins, suggest that deep-water phosphate concentrations may have increased by an order of magnitude without any increase in the rate of P input from the continents. Strikingly, despite a major shift in phosphorite deposition, a new compilation of the phosphorus content of Neoproterozoic and early Paleozoic shows little secular change in median values, supporting the view that changes in remineralization and not erosional P fluxes were the principal drivers of observed shifts in phosphorite accumulation. The trigger for these changes may have been transient Neoproterozoic weathering events whose biogeochemical consequences were sustained by a set of positive feedbacks, mediated by the oxygen and sulfur cycles, that led to permanent state change in biogeochemical cycling, primary production, and biological diversity by the end of the Ediacaran Period.

The geochemistry of rare earth elements and yttrium (REY) in phosphorite has been widely studied. However, the effect of organic matter on REY enrichment has not been well determined. We utilized paired inorganic (δ13Ccarb) and organic (δ13Ccarb) carbon isotopes, total organic carbon (TOC), and REY content (∑REY) of the Zhijin Motianchong (MTC) phosphorite and compared them with those of Meishucun (MSC) phosphorite to reveal the effect of organic matter on REY. The δ13Ccarb of the MTC area (≈0‰) is heavier than that of the MSC area (−5.23‰ to −1.13‰), whereas δ13Corg is lighter (−33.85‰ to −26.34‰) in MTC than in MSC (−32.95‰ to −25.50‰). Decoupled δ13Ccarb and δ13Corg in MTC indicate the contribution of chemoautotrophic organisms or methanotrophic bacteria. Compared to the MSC phosphorite, the MTC phosphorite has higher ∑REY and TOC, and these parameters have a positive relationship. MTC phosphorite has REY patterns resembling those of contemporary organic matter. Furthermore, dolomite cement has a higher ∑REY than dolomite in the phosphorus-bearing dolostone. Additionally, pyrites are located on the surface of fluorapatite in the Zhijin phosphorites. It is reasonable to suggest that the REY was released into the pore water owing to the anaerobic oxidation of organic matter at the interface between seawater and sediment, resulting in the REY enrichment of Zhijin phosphorites.