Search

Weathering crusts after granites are the most important source of heavy rare-earth elements (HREE) worldwide. Although HREE in these deposits is known to be inherited from parental rocks, the origin of HREE enrichment and the reasons why it is rare outside of China remains unclear. Here, we report the occurrence of variably organized nanoparticles of Ce-poor (

The rare earth elements (REE), and in particular neodymium and dysprosium, are essential for the development of renewable energy. At present the REE are sourced from either low concentration weathered granitoid (ion adsorption clay) deposits in southern China, or from high concentration carbonatite-related deposits [1], especially the World’s dominant REE mine at Bayan Obo, China, but also including the Mt Weld weathered carbonatite, Australia. Weathered carbonatites (e.g. Tomtor, Russia; Mount Weld, Australia) are some of the world’s highest grade REE deposits. As part of the NERC Global Partnerships Seedcorn fund project WREED, we have carried out preliminary investigations in weathering products from carbonatite hosted REE deposits. Three end member deposit styles can be identified – in situ residual deposits, where carbonate dissolution has generated primary REE mineral enrichment on palaeosurfaces or in karst; supergene enrichment from dissolution and reprecipitation of REE phosphates and fluorcarbonates forming hydrated phosphates or authigenic carbonate minerals; clay and oxide caps (either from in situ weathering or from soil transport from surrounding rocks) that may hold the REE adsorbed to mineral surfaces (c.f. the ion adsorption deposits). High grade weathered carbonatite deposits typically consist of supergene horizons, that may be phosphate-rich due to dissolution and re-precipitation of apatite and monazite during the weathering process (Mount Weld [2][3]), overlain by later sediments that may be REE enriched by accumulation of residual minerals (e.g. Tomtor [4]). The mineralogy of the ore zone is linked to, but distinct from, the unweathered carbonatite rock, and includes phosphates, crandallite-group minerals, carbonates and fluorcarbonates and oxides. We have carried out leaching studies, SEM examination and XPS characterisation of soil and weathered rock samples from a range of deposits. Residual and supergene processes can result in enrichments up to 100x times bedrock concentrations, with residual enrichments in particular hosted in monazite and bastnäsite. Supergene enrichment results in more complex mineralogy which may present processing challenges. Clay-rich soils have much lower REE concentrations. However, sequential leaching studies demonstrate that a significant proportion of REE are present at trace levels in the oxide fraction in residual and supergene deposits. In clay caps the easily leachable fraction of REE matches that of ion adsorption deposits and may represent a potentially easily extractable resource. References[1] Wall and Chakhmouradian, 2012, Elements 8, 333-340;[2] Duncan and Willett, 1990, Geology of Mineral Deposits of Australia pp. 591-597;[3] Lottermoser, 1990, Lithos 24, 151-167;[4] Kravchenko and Pokrovsky, 1995, Econ. Geol. 90, 676-689

Magnetite (Fe3O4) is one of the most common accessory minerals in magmatic rocks, and it can accommodate a wide variety of major, minor and trace elements that can be measured by laser ablation ICP-MS. In this study, we investigate the chemical compositions of magnetite from four carbonatite complexes (Oka, Mushgai Khudag, Hongcheon and Bayan Obo). The minor elements (Mg, Ti, Al, Mn) in magnetite vary significantly both within and between different complexes. High field strength elements (Zr, Hf, Nb, Ta, U, Th) are generally depleted in magnetite from carbonatite complexes, whereas K, Rb, Cs, Ca and P are commonly below detection limits. V and Zn display significant variations from tens to thousands of ppm. Co, Ni and Ga are present in ppm or tens of ppm, whereas Cu, Sr, Y, Ba and Pb are characterized by sub-ppm levels. Mo and Ge are identified at the ppm level, whereas a consistent concentration of 2–5 ppm is observed for Ge. The determined chemical compositions of magnetite from carbonatite complexes are quite distinguishable compared to those formed in silicate and sulfide melts. This is clearly shown using multielement variation diagrams, and the distinct signatures of carbonatite-related magnetite include strong positive anomalies of Mn and Zn and negative anomalies of Cu, Co and Ga. The discriminant diagrams of Ti vs. Zr + Hf, Ti vs. Nb + Ta and Ni/Cr vs. Ti are applicable for distinguishing magmatic and hydrothermal magnetite in carbonatite-related environments. In addition, the discriminant diagram of Zn/Co vs. Cu/Mo and Cu vs. Zr + Hf can be used to distinguish carbonatite-related magnetite from magnetite that formed in other environments.

This study was carried out in order to find a possible use for waste produced during the processing of vegetables and maize. Anaerobic fermentation is a suitable way to handle this wet and easily biodegradable organic material. The aim of this study was to evaluate the impact of waste corn kernels, peas, crushed corn kernels, French beans, mixed vegetables (broccoli, cauliflower, peas and carrot), corn leaf and corn husk on anaerobic fermentation. Anaerobic fermentation tests was carried out in batch fermenters (5 dm3) for 21 days at 42 °C. During this period the quantity and quality of biogas produced were monitored. The following substrate parameters were determined: dry matter content, organic dry matter content, nutrients content (protein, fat, fibre, starch, acid detergent fibre, neutral detergent fibre) and elemental composition. The hypothesis predicting the inhibitory impact of substrates on the anaerobic process was not confirmed. Biogas production after 21 days of hydraulic retention time ranged from 0.6773 m3/kg of organic dry matter (peas) to 1.1108 m3/kg of organic dry matter (mixed vegetables). All substrates had the final concentration of methane in the biogas ranged from 59.43 to 65.97%vol. The hypothesis about the impact of pre-treatment of substrates (crushing) on the quantity of the biogas produced was confirmed. The biogas production from the crushed corn kernel was significantly higher than the biogas production from substrates with a similar composition of nutrients (corn kernel, peas). Vegetables and maize waste produced during processing is a suitable substrate for anaerobic fermentation.

Rare earth elements (REEs) are considered critical elements in modern society due to their irreplaceable role in new innovative and energy technologies. The giant carbonatite-related Bayan Obo deposit contributes most REE resources in the world’s market, while its origin is still unclear because of the complicated and diverse REE ore mineralogy and texture. Thescanning electron mircroscopy SEM)-based automated mineralogy allows for the numeric assessment of rocks and ores’ compositional and textural properties. Here, we use TIMA (TESCAN Integrated Mineral Analyzer) to quantitatively characterize REE ore mineralogy from the deep drill core within the H8 unit (“dolomite marble”) to better understand the deposit. The mineral composition, occurrence, and Ce elemental deportment of the borehole ores at different depths (i.e., 1107 m, 1246 m, 1406 m, 1546 m, and 1682 m) were obtained. The results show that the main types of ores in the investigated samples can be divided into banded REE-Fe ores, banded REE ores, disseminated REE-Fe ores, and veined REE ores. REE and gangue minerals vary significantly in abundance and occurrence. Monazite-(Ce) and bastnäsite-(Ce) are the primary REE host minerals, and both contribute the most to the REE budget. Other REE minerals, such as parisite-(Ce)/synchysite-(Ce), cerite-(Ce), huanghoite-(Ce)/cebaite-(Ce), and aeschynite-(Ce), are significant contributors. The gangue minerals generally include fluorite, barite, magnetite, pyrite, quartz, magnesio-arfvedsonite, and minerals of the biotite and apatite groups, among others. Combined with the newly published mineral-scale chronological and isotopic geochemical analyses, it is reasonable to conclude that the later hydrothermal fluids remobilized and redistributed the original Mesoproterozoic carbonatitic REE minerals and formed a high variable ore mineral assemblage. Furthermore, it is demonstrated that the mineralogical study using TIMA can provide accurate and reliable mineralogy data for the comprehensive interpretation of the complex REE ores, and extend our understanding of the deposit.

The presented study deals with the observation of properties of methicillin-susceptible Staphylococcus aureus (MSSA) and methicillin-resistant S. aureus (MRSA) in the toxic arsenic environment and influence of arsenic on antioxidant capacity. Two forms of arsenic (As(III), As(V)) with different concentrations were used for induction of the oxidative stress in tested strains. Microbiological methods showed that the growth inhibition of MSSA was higher than that of MRSA in presence of both arsenic ions. As(III) showed 24% and 33% higher anti-microbial effects than As(V) against MSSA and MRSA respectively. A similar result was found also in the experiment of reduction of biofilm-formation. By using spectrophotometry, it was revealed that As(III) induced higher antioxidant production in both bacterial cultures. Methicillin-susceptible S. aureus produced an app. 50 mg equivalent of gallic acid (GAE/1 mg of protein) and MRSA produced an app. 15 mg of GAE/1 mg of protein. The productions of metallothionein in MSSA and MRSA were decreased up to 62.41% and 55.84% respectively in presence of As ions. Reduction of As(III) and As(V) concentrations leads to a decrease in antioxidant production and increased the formation of metallothionein. All of these changes in the results were found to be significant statistically. Taken together, these experiments proved that in comparison with MSSA, MRSA is less susceptible not only to the antimicrobial effects of antibiotics but also against effects caused by metalloids, as arsenic. Thus, it can be stated that MRSA abounds with complex defensive mechanisms, which may in the future constitute significant problem in the efficiency of antibiotics alternatives as metal ions or nanoparticles.

Glucose is a typical diagnostic marker of diabetes mellitus but it may be also helpful during diagnosis of some types of poisoning, immunological disorder or long-term stress at hospitalized patients. Diagnosis of diabetes mellitus in time is indispensable for prevention of life-threatening complication and so, accurate and easy device for non-invasive and accurate self-diagnosis is necessary. Simple assay based on filter paper with chitosan layer and with immobilized enzymes glucose oxidase and peroxidase and phone camera detection has been proposed for home-care glucose detection in urine. Data were processed in RGB (red–green–blue) color model when blue color channel showed the best sensitivity to changing glucose concentrations. Assay exerted linear regression from 0 to 4 mmol/l and limit of detection was set to be 166 µmol/l. Assay was not influenced by any interfering substances including maltose, sucrose, sorbitol or fructose or by urine matrix substance such as bovine serum albumin, ascorbic acid, uric acid or urea. Measurement of glucose from spiked urine samples reveals also no influence of the matrix on the assay. Long-term stability was measured and filter papers coated by enzymes showed excellent stability for at least 9 weeks without any special treatment or package. In comparison with differently modified filter paper, filter paper with both chitosan and enzymes showed the best sensitivity to changing glucose concentration. In a conclusion, simple (phone camera detection) and fast (3-min reaction) assay for quantitative detection of glucose from urine was optimized.

The silico-carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartzbearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnasite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Burbankite was also potentially an early crystallising phase. Monazite-(Ce) was subsequently altered to produce a second generation of apatite, which was in turn replaced and overgrown by britholite-(Ce), accompanied by the formation of allanite-(Ce). Bastnasite and parisite where replaced by synchysite-(Ce) and rontgenite-(Ce). Aeschynite-(Ce) was altered to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution re carbonatite, to more silica-rich conditions during early hydrothermal processes, to fully hydrothermal conditions accompanied by the formation of sulphateminerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE.Mass balance considerations indicate hydrothermal HREE to themineralisation. The evolution of the in may have been the HREE source. Leaching in the presence of strong, LREE-selective ligands (Cl for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferentialHREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during alteration, and hence sulphate complexationmay have been important for preferential HREE transport. AlongsideHREE-enrichedmagmatic sources, and enrichment during magmatic processes, late stage alteration with non-LREE-selective ligands may be critical in forming HREE-enriched carbonatites.flects the evolution from magmaticfluids must have contributedfluorcarbonate mineral assemblage requires an increaseaCa2+ and aCO3 2− in the metasomatic fluid (where a is activity), and breakdown of HREE-enriched calcite−) may account

Eu(III) and Tb(III) Schiff base complexes are applicable in various fields such as sensing, assays, screening protocols in vitro, and imaging studies in vitro or in vivo. Fluorescent europium and terbium complexes and their interaction with cell penetrating peptide (KKKRKC) can represent an excellent key for understanding pathway of peptide transportation though cell membrane and the application of Schiff base complexes as potential antibacterial drugs. The Schiff base–metal complexes and its conjugates with peptide were tested for their antibacterial activity against Pseudomonas aeruginosa and Salmonella typhimurium. Schiff base–metal complexes conjugated with peptide show minor toxicity in normal human PNT1A cells and high antibacterial activity against P. aeruginosa and S. typhimurium, where IC50 down to 125.9 and/or 36.1 µM were found for P. aeruginosa and S. typhimurium, respectively. Our results strongly suggest that Schiff base–metal complexes conjugated with peptide have great potential to be developed into highly effective antibacterial drug.

Mesozoic granites in the Nanling region, South China, are important primary rocks for ion-adsorption rare earth element (REE) deposits. Moreover, metallic deposits of W, Sn, Nb and Ta also develop in these granites, most of which formed in the Late Jurassic . The Qingxi and Guanxi granites in the Nanling region contain abundant REE minerals and have zircon U-Pb ages of 223.0 ± 0.7 Ma and 198.8 ± 1.4 Ma, respectively. They are of metaluminous to slightly peraluminous in character having a high K calc-alkaline composition, and have high K2O + Na2O and FeOT + MgO contents and a Ga/Al ratio similar to A-type granites. These granites plot into the post-collision field, similar to the A2-type granites. The Qingxi and Guanxi granites indicate a crust-dominant origin by having high levels of Rb and Th relative to Nb and Ta normalized to ocean-ridge granites. They are characterized by LREE enrichment and the majority of REE accumulating in the primary REE minerals include REE-phosphates and fluorocarbonates. The Guanxi rocks have a stronger negative Eu anomaly, but lower REE composition than the Qingxi granites, implying that the basement may have played an important role in the REE mineralization rather than fractional crystallization . This further implies that the basement in South China may have been subjected to different evolutionary geodynamics , resulting in different multi-metallic mineralization of W-Sn-Nb-Ta-REE hosted by large scale Mesozoic granites.

Nanobiosynthesis belongs to the most recent methods for synthesis of nanoparticles. This type of synthesis provides many advantages including the uniformity in particle shape and size. The biosynthesis has also a significant advantage regarding chemical properties of the obtained particles. In this study, we characterized the basic properties and composition of quantum dots (QDs), obtained by the extracellular biosynthesis by Escherichia coli. Furthermore, the toxicity of the biosynthesized QDs was compared to QDs prepared by microwave synthesis. The obtained results revealed the presence of cyan CdTe QDs after removal of substantial amounts of organic compounds, which stabilized the nanoparticle surface. QDs toxicity was evaluated using three cell lines Human Foreskin Fibroblast (HFF), Human Prostate Cancer cells (PC-3) and Breast Cancer cells (MCF-7) and the MTT assay. The test revealed differences in the toxicity between variants of QDs, varying about 10% in the HFF and 30% in the MCF-7 cell lines. The toxicity of the biosynthesized QDs to the PC-3 cell lines was about 35% lower in comparison with the QDs prepared by microwave synthesis.

The Lugiin Gol nepheline syenite intrusion, Mongolia, hosts a range of carbonatite dikes mineralized in rare-earth elements (REE). Both carbonatites and nepheline syenite-fluorite-calcite veinlets are host to a previously unreported macroscale texture involving pseudo-graphic intergrowths of fluorite and calcite. The inclusions within calcite occur as either pure fluorite, with associated REE minerals within the surrounding calcite, or as mixed calcite-fluorite inclusions, with associated zirconosilicate minerals. Consideration of the nature of the texture, and the proportions of fluorite and calcite present (∼29 and 71 mol%, respectively), indicates that these textures most likely formed either through the immiscible separation of carbonate and fluoride melts, or from cotectic crystallization of a carbonate-fluoride melt. Laser ablation ICP-MS analyses show the pure fluorite inclusions to be depleted in REE relative to the calcite. A model is proposed, in which a carbonate-fluoride melt phase enriched in Zr and the REE, separated from a phonolitic melt, and then either unmixed or underwent cotectic crystallization to generate an REE-rich carbonate melt and an REE-poor fluoride phase. The separation of the fluoride phase (either solid or melt) may have contributed to the enrichment of the carbonate melt in REE, and ultimately its saturation with REE minerals. Previous data have suggested that carbonate melts separated from silicate melts are relatively depleted in the REE, and thus melt immiscibility cannot result in the formation of REE-enriched carbonatites. The observations presented here provide a mechanism by which this could occur, as under either model the textures imply initial separation of a mixed carbonate-fluoride melt from a silicate magma. The separation of an REE-enriched carbonate-fluoride melt from phonolitic magma is a hitherto unrecognized mechanism for REE-enrichment in carbonatites, and may play an important role in the formation of shallow magmatic REE deposits. Keywords: Silicate-carbonate-fluoride melt immiscibility, Carbonatite, Alkaline syenite, Shallow REE deposit, Lugiin Gol, Mongolia

MS, AF and FW acknowledge the support of the NERC SoS:RARE consortium grant (NE/M011267/1). D. Kavecsanszki acknowledges the support of a postgraduate fellowship from the College of Engineering, Mathematics and Physical Sciences at the University of Exeter. The rare earth elements are unusual when defining giant-sized ore deposits, as resources are often quoted as total rare earth oxide, but the importance of a deposit may be related to the grade for individual, or a limited group of, the elements. Taking the total REE resource, only one currently known deposit (Bayan Obo) would class as giant (>1.7×107 tonnes contained metal), but a range of others classify as large (>1.7×106 tonnes). With the exception of unclassified resource estimates from the Olympic Dam IOCG deposit, all of these deposits are related to alkaline igneous activity – either carbonatites or agpaitic nepheline syenites. The total resource in these deposits must relate to the scale of the primary igneous source, but the grade is a complex function of igneous source, magmatic crystallisation, hydrothermal modification and supergene enrichment during weathering. Isotopic data suggest that the sources conducive to the formation of large REE deposits are developed in subcontinental lithospheric mantle, enriched in trace elements either by plume activity, or by previous subduction. The reactivation of such enriched mantle domains in relatively restricted geographical areas may have played a role in the formation of some of the largest deposits (e.g. Bayan Obo). Hydrothermal activity involving fluids from magmatic to meteoric sources may result in the redistribution of the REE and increases in grade, depending on primary mineralogy and the availability of ligands. Weathering and supergene enrichment of carbonatite has played a role in the formation of the highest grade deposits at Mount Weld (Australia) and Tomtor (Russia). For the individual REE with the current highest economic value (Nd and the HREE), the boundaries for the large and giant size classes are 2 orders of magnitude lower, and deposits enriched in these metals (agpaitic systems, ion absorption deposits) may have significant economic impact in the near future. Publisher PDF

The effects of ultrasonic milling, dry and wet ball milling, and vibro-milling on the particulate properties, crystalline characteristics, morphology, and surface area of clinoptilolite (Cpt) have been investigated. Laser beam scattering technique, X-ray diffraction (XRD), scanning electron microscopy (SEM), and nitrogen adsorption/desorption at 77 K are used to characterize the initial and ground Cpt powders. Results show that Cpt particle size is significantly reduced by all carried out milling methods in which vibro-milling could produce particles with diameter less than 100 nm. The size distribution of Cpt is remarkably narrowed by using vibro- and wet ball milling. The crystallinity of Cpt noticeably decreases for the samples obtained by ball milling while vibro- and ultrasonic millings show a negligible effect on crystallinity. The specific surface area of Cpt is enhanced by all four milling methods.

Carbonatites are abundant in the rare earth elements (REE), and they host the most important REE resources in the world. However, the mechanisms that concentrate these elements during carbonatitic magmatic processes are still poorly constrained. Here, we report the occurrence of apatite-hosted melt inclusions from the Ulgii Khiid carbonatites, Mongolia, and use these to reconstruct the evolution of REE concentrations and patterns in early, primary carbonatite magma. The melt inclusions consist of a varied polycrystalline assemblage of daughter minerals, including calcite, diopside, phlogopite, magnetite, pyrite, monazite, parisite, and a phosphate glass which is remarkably enriched in REE. Heating-quenching experiments show that the homogenization temperatures of the inclusions are above 1200 °C and produce three immiscible liquid phases (i.e., phosphate-, silicate-, and Fe-silicate-melt). The phosphate melt has much higher REE content than the silicate melts. We, therefore, suggest that the melt inclusions trapped a REE-, P- and silicate-enriched carbonate melt produced via carbonate-silicate liquid immiscibility. During this process, both REE and P preferentially incorporated into the carbonate melt. With subsequent crystal fractionation of REE- and P-poor carbonate and silicate minerals, the separated carbonatitic melt becomes P-REE-saturated, forming REE minerals and an immiscible REE-rich phosphate melt. The phosphate melt is highly efficient at concentrating REE during the immiscibility process and plays a crucial role in controlling the REE budget in the P-rich carbonatite magmas.

The South Qinling orogen in central China hosts carbonatites occurring as stocks associated with syenites and collectively regarded as the Miaoya intrusive complex. The complex hosts economic resources of rare-earth elements (REE) and Nb. The Miaoya syenites are strongly metasomatized at the contact with the carbonatites and cross-cut by carbonate and felsic veinlets. Small oscillatory-zoned crystals of zircons from the syenites give a concordant U–Pb age of 147 ± 0.5 Ma, which differs significantly from the ages of both large magmatic zircon grains from the syenites and primary monazite from the carbonatites (766 Ma and 234 Ma, respectively). To account for the possibility that the Miaoya syenites are coeval and cogenetic with the carbonatites, the trace-element budget of both rock types was examined in detail. The Miaoya carbonatite contains primary REE-rich fluorapatite and monazite, which precipitated earlier than the rock-forming REE-poor calcite, indicating that the primary carbonatitic magma was rich in REE. The compositions of the parental syenitic and carbonatitic magmas, calculated on the basis of the trace-element composition of primary fluorapatite in the two rock suites, show that the carbonatitic magma contained higher Sr and REE (La–Tb), but lower Ba, Pb, Th, U, Nb and Ta levels in comparison with the syenitic melt. These differences are inconsistent with derivation of the Miaoya rocks from a homogeneous carbonate–silicate melt by immiscibility or crystal fractionation. It is therefore concluded that the carbonatitic magma at Miaoya was generated directly in the mantle. Emplacement of the carbonatites in the South Qinling orogen marked transition to a postorogenic regime, and was preceded by oceanic crust subduction and closure of the Mianlue Ocean in the Triassic. Our models show that melting of the Mianlue crust and up to 10 wt.% of sediments cannot produce the levels of REE enrichment observed in the Miaoya carbonatites. More complex models, involving recycling of the Mianlue oceanic crust and a REE-rich carbonate liquid from an old deep-seated mantle source are required to explain the observed trace-element characteristics of the Miaoya carbonatites.

The sources and formation conditions of unconventional Zr–Nb–REE mineralisation (REE = rare earth elements) presently found in increasing number worldwide are still poorly constrained. One particular problem is the specific role of magmatic and hydrothermal processes active in various geological settings. Investigation of Zr–Nb–REE mineralisation at Khalzan Buregte and Tsakhir, Western Mongolia, enables to evaluate magmatic processes preceding economic mineralisation and, in a second step, to compare similar ore-forming processes developing in host rocks of contrasting rock composition (low- vs. high-silica rocks). The genesis of the Zr–Nb–REE mineralisation is re-assessed using field observations, whole rock analysis (chemical composition, quantitative modal analysis by X-ray diffraction) and by the application of various transmitted light and electron microscopic techniques. Coarse-grained intrusive bodies, dikes and volcanic rocks of alkaline, silica-saturated composition were found to be contemporarily emplaced at subvolcanic to volcanic levels forming four alkaline massifs within the Khalzan Buregte area. The whole rock composition of weakly altered magmatic rocks ranges from syenite to quartz monzonite and alkaline granite (alkali feldspar syenite to alkali feldspar granite according to their modal composition). Magmatic and at least two subsequent hydrothermal processes contributed significantly to the formation of economic concentrations of high field strength elements (HFSE) such as Zr, Hf, Nb, Ta, REE and Y in the Khalzan Buregte deposit and in the nearby Tsakhir prospect. Mixing of magma from at least three sources and the formation of potassium feldspar cumulates resulted in local enrichment of Zr, Nb and light rare earth elements (LREE) in the rocks up to sub-economic levels. There was no significant increase in Y and heavy rare earth elements (HREE) during magmatism. Multistage metasomatic alteration resulted in a pronounced chemical and mineralogical heterogeneity of associated alteration assemblages. The main hosts of Zr and Hf in the ores are zircon and other zirconium silicates (gittinsite, catapleiite-(Ca) and elpidite). The rare metals Nb and Ta are mainly contained in various types of pyrochlore (Khalzan Buregte) and, to a lesser extent, in fergusonite and other minerals (Tsakhir). A large variety of REE- and Y-bearing minerals have been identified, including oxides, fluorocarbonates and silicates. Early hydrothermal alteration by silica- and carbonate-rich fluids yielded extreme concentrations of Zr, Nb and LREE. Later alteration resulted in enrichment of Y and HREE. In the latter case, fluids were very rich in fluorine. Our preliminary genetic model assumes a carbonatite-related fluid system responsible for the early alteration that occurred late during or postdating the intrusion/extrusion of the silica-saturated magmas. A “Li-F granite-type” fluid system was active during the late alteration. The interplay of all these processes resulted in the formation of a complex, economic Zr–Nb–REE mineralisation at Khalzan Buregte.

The Huanglongpu carbonatite-related Mo ore field is located in the Lesser Qinling Orogenic belt in the southern margin of the North China block. The ore field is composed of six deposits, Yuantou, Wengongling, Dashigou, Shijiawan, Taoyuan and Erdaohe, all of which are genetically related to carbonatite dykes except for the Shijiawan deposit which is associated with a granitic porphyry. The Yuantou carbonatite dykes intruded into Archean gneiss and other carbonatites emplaced into Mesoproterozoic volcanic and sediment rocks. The carbonatites are mainly composed of calcite and variable amounts of quartz and K-feldspar and minor molybdenite. Re–Os dating of molybdenite from the Yuantou carbonatite yields a weighted average age of 225.0 ± 7.6 Ma, consistent with the molybdenite age (221 Ma) from the Dashigou deposit. The rocks are characterized by high heavy REE (HREE) contents and consistent flat REE distribution patterns with La/Ybcn ~ 1. Quartz in the carbonatites from Yuantou and Dashigou deposits shows consistent O isotopes (8.1–10.2‰) similar to the associated calcite (7.2–9.5‰). The quartz and associated K-feldspar contain lower Zr, Hf and higher HREE abundances and negligible Eu anomaly relative to those from the granite porphyry in Shijiawan. Both minerals are primary products in the carbonatitic liquid, and not captured from the wall-rocks or crustal-derived silicate magmas, or a hydrothermal origin. Thus, the Huanglongpu carbonatitic liquids were enriched in Si and Mo, which may be produced by intensely fractional crystallization of non-silicate minerals.

Mineralization with ion adsorption rare earth elements (REEs) in the weathering profile of granitoid rocks from Nanling region of Southeast China is an important REE resource, especially for heavy REE (HREE) and Y. However, the Jurassic granites in Zhaibei which host the ion adsorption light REE (LREE) ores are rare. It is of peraluminous and high K calc-alkaline composition, which has similar geochemical features of high K2O + Na2O and Zr + Nb + Ce + Y contents and Ga/Al ratio to A-type granite. Based on the chemical discrimination criteria of Eby [Geology 20 (1992) 641], the Zhaibei granite belongs to A1-type and has similar source to ocean island basalts. The rock is enriched in LREE and contains abundant REE minerals including LREE-phosphates and halides. Minor LREE was also determined in the feldspar and biotite, which shows negligible and negative Eu anomalies, respectively. This indicates that the Zhaibei granite was generated by extreme differentiation of basaltic parent magmas. In contrast, granites associated with ion adsorption HREE ores contain amounts of HREE minerals, and show similar geochemical characteristics with fractionated felsic granites. Note that most Jurassic granitoids in the Nanling region contain no REE minerals and cannot produce REE mineralization. They belong to unfractionated M-, I- and S-type granites. Therefore, accumulation of REE in the weathering profile is controlled by primary REE mineral compositions in the granitoids. Intense fractional crystallization plays a role on REE enrichment in the Nanling granitoid rocks.

Oxidative stress is a pathological process related to not only animal kingdom but also plants. Regarding oxidative stress in plants, heavy metals are frequently discussed as causative stimuli with relevance to ecology. Because heavy metals have broad technological importance, they can easily contaminate the environment. Much of previous effort regarding the harmful impact of the heavy metals was given to their toxicology in the animals and humans. Their implication in plant pathogeneses is less known and remains underestimated.The current paper summarizes basic facts about heavy metals, their distribution in soil, mobility, accumulation by plants, and initiation of oxidative stress including the decline in basal metabolism. The both actual and frontier studies in the field are summarized and discussed. The major pathophysiological pathways are introduced as well and link between heavy metals toxicity and their ability to initiate an oxidative damage is provided. Mobility and bioaccessibility of the metals is also considered as key factors in their impact on oxidative stress development in the plant. The metals like lead, mercury, copper, cadmium, iron, zinc, nickel, vanadium are depicted in the text.Heavy metals appear to be significant contributors to pathological processes in the plants and oxidative stress is probably an important contributor to the effect. The most sensitive plant species are enlisted and discussed in this review. The facts presented here outline next effort to investigate pathological processes in the plants.

The main mechanism of action of platinum-based cytostatic drugs – cisplatin, oxaliplatin and carboplatin – is the formation of DNA cross-links, which restricts the transcription due to the disability of DNA to enter the active site of the polymerase. The polymerase chain reaction (PCR) was employed as a simplified model of the amplification process in the cell nucleus. PCR with fluorescently labelled dideoxynucleotides commonly employed for DNA sequencing was used to monitor the effect of platinum-based cytostatics on DNA in terms of decrease in labeling efficiency dependent on a presence of the DNA-drug cross-link. It was found that significantly different amounts of the drugs - cisplatin (0.21 μg/mL), oxaliplatin (5.23 μg/mL), and carboplatin (71.11 μg/mL) - were required to cause the same quenching effect (50%) on the fluorescent labelling of 50 μg/mL of DNA. Moreover, it was found that even though the amounts of the drugs was applied to the reaction mixture differing by several orders of magnitude, the amount of incorporated platinum, quantified by inductively coupled plasma mass spectrometry, was in all cases at the level of tenths of μg per 5 μg of DNA.

Sulfur mustard, in a chemical name bis(2-chloroethyl) sulfide, is a chemical warfare agent. It is cytotoxic and blister forming once spread over the skin. Though exact molecular mechanism of sulfur mustard toxic action remains unknown, inflammation and oxidative stress development are considered as the most relevant pathological consequences. Applications of either low-molecular weight antioxidants or cofactors for enzymatic antioxidants are considered as suitable ways how to ameliorate the poisoning. In this article, survey of literature on countermeasures against sulfur mustard poisoning are given and evidence of oxidative stress role during sulfur mustard poisoning and availability of antioxidants for the therapy are discussed.

Oxidative stress is a pathological process related to not only animal kingdom but also plants. Regarding oxidative stress in plants, heavy metals are frequently discussed as causative stimuli with relevance to ecology. Because heavy metals have broad technological importance, they can easily contaminate the environment. Much of previous effort regarding the harmful impact of the heavy metals was given to their toxicology in the animals and humans. Their implication in plant pathogeneses is less known and remains underestimated.

Many carbonatites are associated both spatially and temporally with large igneous provinces (LIPs), and considered to originate from a mantle plume source lacking any contribution from recycled crustal materials. Here, we report an occurrence of carbonatite enriched in rare-earth elements (REE) and associated with the Tarim LIP in northwestern China. The Tarim LIP comprises intrusive and volcanic products of mantle plume activity spanning from ~ 300 to 280 Ma. The carbonatites at Wajilitage in the northwestern part of Tarim are dominated by calcite and dolomite varieties, and contain abundant REE minerals (principally, monazite and REE-fluorcarbonates). Th–Pb age determination of monazite yielded an emplacement age of 266 ± 5.3 Ma, i.e. appreciably younger than the eruption age of flood basalts at ~ 290 Ma. The carbonatites show low initial 87Sr/86Sr (0.7037–0.7041) and high eNd(t) (1.2–4) values, which depart from the isotopic characteristics of plume-derived basalts and high-Mg picrites from the same area. This indicates that the Wajilitage carbonatites derived from a mantle source isotopically distinct from the one responsible for the voluminous (ultra)mafic volcanism at Tarim. The carbonatites show δ26MgDSM3 values (− 0.99 to − 0.65‰) that are significantly lower than those in typical mantle-derived rocks and rift carbonatites, but close to marine sediments and orogenic carbonatites. We propose that the carbonatites in the Tarim LIP formed by decompressional melting of recycled sediments mixed with the ambient mantle peridotite. The enriched components in the Tarim plume could be accounted for by the presence of recycled sedimentary components in the subcontinental mantle.

Nowadays increasing attention has been focused on polyphenolic compounds as the main representants of antioxidants in horticultural crops including fruits. The edible honeysuckle has an unique position among lesser known fruits due to its high level of antioxidants. In the present study we determined polyphenolic profile and antioxidant capacity of four Russian cultivars of edible honeysuckle including ‘Gerda 25’, ‘Amfora’, ‘Morena’, ‘Lipnicka’, which found together in a single location in Mendel University in Brno, The Czech Republic. Polyphenolic compounds were detected by high performance liquid chromatography coupled with electrochemical detector (HPLC-ED). The antioxidant capacity was measured by DPPH test. According to the results there were differences among cultivars in terms of polyphenolic content and antioxidant activity and Lonicera kamtschatica ‘Gerda 25’ were found to be possessed the highest content of phenolic compounds corresponding to the highest value of antioxidant activity.

Most studies of compositional heterogeneities in the mantle, related to recycling of crustal sediments or delaminated subcontinental lithosphere, come from oceanic setting basalts. In this work, we present direct geochronological and geochemical evidence for the incorporation of recycled crustal materials in collision-related carbonatites of the South Qinling orogenic belt (SQ), which merges with the Lesser Qinling orogen (LQ) to separate the South and North China Blocks. The SQ carbonatites occur mainly as stock associated with syenites. The data presented here show that zircon from the syenites yields an age of 766 ± 25 Ma, which differs significantly from the age of primary monazite from the carbonatites (233.6 ± 1.7 Ma). The syenites contain lower initial 87Sr/86Sr and higher eNd values. This indicates that the carbonatites do not have genetically related with the silicate rocks, and were directly derived from a primary carbonate magma generated in the mantle. The carbonatites show a Sr–Nd isotopic signature similar to that of the chondritic uniform reservoir (CHUR), and parallel Sm–Nd model ages (TCHUR) of 190–300 Ma. However, the rocks have extremely variable Pb isotopic values straddling between the HIMU and EM1 mantle end-members. Most carbon and oxygen isotopic compositions of the SQ carbonatites plot outside the field for primary igneous carbonates. Their δ13C shows higher value than a ‘normal’ mantle, which implies an incorporation of recycled inorganic carbon. The carbonatites were emplaced close to the Mianlue suture, and followed the closure of the Mianlue ocean and Triassic collision of the South and North China Blocks. However, direct melting of the subducted Mianlue oceanic crust characterized by high eNd and low (EM1-like) 206Pb/204Pb values cannot explain the CHUR-like Nd signature and the Pb isotopic trend toward HIMU in the SQ carbonatites. We conclude that their parental magma was derived from a source incorporating the Mianlue oceanic crust mixed with an asthenospheric (or deeper) material characterized by high Pb and low Nd isotopic values. This material represents a deep-seated Proterozoic carbonate component recycled via mantle convection or localized upwelling. Notably, this model cannot explain the isotopic compositions of the Late Triassic (209–221 Ma) carbonatites in the LQ, characterized by a mantle-derived δ13C, but EM1-like Sr–Nd–Pb isotopic compositions. This signature is best explained in terms of delamination of the lower continental crust thickened during the collision of the South and North China Blocks, and partial incorporation of the delaminated material into the LQ mantle source. Modeling of the measured Sr–Nd–Pb isotopic variations suggests that the source of the LQ carbonatites could be produced by mixing of 80–85% of mantle material and 15–20% of delaminated lower continental crust. The emplacement of the SQ and LQ carbonatites marked a gradual transition from a compressional tectonic regime, brought about by the collision of the South and North China Blocks to intra-orogenic extension in the waning stages of the Triassic orogeny.

The nanotechnological concept is based on size-dependent properties of particles in the 1–100 nm range. Nevertheless, the connection between their size and effect is still not clear. Thus, we focused on reductive colloidal synthesis, characterization and biological testing of Pt nanoparticles (PtNPs) capped with biocompatible polymer polyvinylpyrrolidone (PVP). Synthesized PtNPs were of 3 different primary sizes (approx. ∼10; ∼14 and > 20 nm) and demonstrated exceptional haemocompatibility. In vitro treatment of three different types of malignant cells (prostate – LNCaP, breast – MDA-MB-231 and neuroblastoma – GI-ME-N) revealed that even marginal differences in PtNPs diameter resulted in changes in their cytotoxicity. The highest cytotoxicity was observed using the smallest PtNPs-10, where 24IC 50 was lower (3.1–6.2 μg/mL) than for cisplatin (8.1–19.8 μg/mL). In contrast to MDA-MB-231 and LNCaP cells, in GI-ME-N cells PtNPs caused noticeable changes in their cellular structure without influencing their viability. Post-exposure analyses revealed that PtNPs-29 and PtNPs-40 were capable of forming considerably higher amount of reactive oxygen species with consequent stimulation of expression of metallothionein (MT1/2 and MT3), at both mRNA and protein level. Overall, our pilot study demonstrates that in the nanoscaled world even the smallest differences can have crucial biological effect.

Interactions of silver phosphate nanoparticles (SPNPs) and selenium nanoparticles (SeNPs) with Staphylococcus aureus cultures have been studied at the cellular, molecular and protein level. Significant antibacterial effects of both SPNPs and SeNPs on S. aureus were observed. At a concentration of 300 μM, SPNPs caused 37.5% inhibition of bacterial growth and SeNPs totally inhibited bacterial growth. As these effects might have been performed due to the interactions of nanoparticles with DNA and proteins, the interaction of SPNPs or SeNPs with the amplified zntR gene was studied. The presence of nanoparticles decreased the melting temperatures of the nanoparticle complexes with the zntR gene by 23% for SeNPs and by 12% for SPNPs in comparison with the control value. The concentration of bacterial metallothionein was 87% lower in bacteria after application of SPNPs (6.3 μg mg(-1) protein) but was increased by 29% after addition of SeNPs (63 μg mg(-1) protein) compared with the S. aureus control (49 μg mg(-1) protein). Significant antimicrobial effects of the nanoparticles on bacterial growth and DNA integrity provide a promising approach to reducing the risk of bacterial infections that cannot be controlled by the usual antibiotic treatments.

Nucleic acids belong to the most important molecules and therefore the understanding of their properties, function and behavior is crucial. Even though a range of analytical and biochemical methods have been developed for this purpose, one common step is essential for all of them – isolation of the nucleic acid from the from complex sample matrix. The use of magnetic particles for the separation of nucleic acids has many advantages over other isolation methods. In this study, an isolation procedure for extraction of DNA was optimized. Each step of the isolation process including washing, immobilization and elution was optimized and therefore the efficiency was increased from 1.7% to 28.7% and the total time was shortened from 75 to 30 min comparing to the previously described method. Quantification of the particular parameter influence was performed by square-wave voltammetry using hanging drop mercury electrode. Further, we compared the optimized method with standard chloroform extraction and applied on isolation of DNA from Staphylococcus aureus and Escherichia coli.

Carcinoma of prostate (CaP) is the second most frequent malignant tumor occurring in men in Europe. Currently there is discussion on a wide range of potential CaP markers. One of them-nonprotein amino acid sarcosine, also known as N-methylglycine was chosen as a challenge for the development of microfluidic system with isolation by modified paramagnetic microparticles. Therefore, the aim of this study was to design a low-cost, simple, and rapid microfluidic system based on sarcosine isolation with modified paramagnetic microparticles and subsequent analysis on the ion exchange LC. We modified Dowex microparticles with Fe2O3 nanoparticles. Our paramagnetic microparticles were able to establish the binding with sarcosine. Moreover, we designed microfluidic device for sarcosine determination. Analysis of samples was carried out with LOD of 1 uM of a sarcosine that is sufficient because it is similar to concentrations of a sarcosine observed in the CaP patients.

Volcanic-plutonic alkaline complexes from Lugiin Gol, Mushgai Khudag and Bayan Khoshuu, southern Mongolia (244, 139 and 131 Ma, respectively) occur within grabens in E-W lineaments. They are represented by syenitic rock-types (silica undersaturated to slightly silica oversaturated) potassic rocks and are associated to stockworks of carbonatitic veins, dykes and so on. Geochemical characteristics and isotope systematics point to a veined mantle source particularly enriched in LILE and LREE. The carbonatitic veins show high contents of Ba, Sr, Th and REE and are suitable as potential ore deposits.

Pathogenic bacteria have become a serious socio-economic concern. Immunomagnetic separation-based methods create new possibilities for rapidly recognizing many of these pathogens. The aim of this study was to use superparamagnetic particles-based fully automated instrumentation to isolate pathogen Staphylococcus aureus and its Zn(II) containing proteins (Zn-proteins). The isolated bacteria were immediately purified and disintegrated prior to immunoextraction of Zn-proteins by superparamagnetic beads modified with chicken anti-Zn(II) antibody. S. aureus culture was treated with ZnCl(2). Optimal pathogen isolation and subsequent disintegration assay steps were carried out with minimal handling. (i) Optimization of bacteria capturing: Superparamagnetic microparticles composed of human IgG were used as the binding surface for acquiring live S. aureus. The effect of antibodies concentration, ionic strength, and incubation time was concurrently investigated. (ii) Optimization of zinc proteins isolation: pure and intact bacteria isolated by the optimized method were sonicated. The extracts obtained were subsequently analyzed using superparamagnetic particles modified with chicken antibody against zinc(II) ions. (iii) Moreover, various types of bacterial zinc(II) proteins precipitations from particle-surface interactions were tested and associated protein profiles were identified using SDS-PAGE. Use of a robotic pipetting system sped up sample preparation to less than 4 h. Cell lysis and Zn-protein extractions were obtained from a minimum of 100 cells with sufficient yield for SDS-PAGE (tens ng of proteins). Zn(II) content and cell count in the extracts increased exponentially. Furthermore, Zn(II) and proteins balances were determined in cell lysate, extract, and retentate.

Carbonatites, usually occurring within intra-continental rift-related settings, have strong light rare earth element (LREE) enrichment; they rarely contain economic heavy REE (HREE). Here, we report the identification of Late Triassic HREE-Mo-rich carbonatites in the northernmost Qinling orogen. The rocks contain abundant primary HREE minerals and molybdenite. Calcite-hosted fluid inclusions, inferred to represent a magmatic-derived aqueous fluid phase, contain significant concentrations of Mo (~17 ppm), reinforcing the inference that these carbonatitic magmas had high Mo concentrations. By contrast, Late Triassic carbonatites in southernmost Qinling have economic LREE concentrations, but are depleted in HREE and Mo. Both of these carbonatite types have low δ26Mg values (−1.89 to −1.07‰), similar to sedimentary carbonates, suggesting a recycled sediment contribution for REE enrichment in their mantle sources. We propose that the carbonatites in the Qinling orogen were formed, at least in part, by the melting of a subducted carbonate-bearing slab, and that 10 Ma younger carbonatite magmas in the northernmost Qinling metasomatized the thickened eclogitic lower crust to produce high levels of HREE and Mo.

Panxi region in west Sichuan province is one of the most economically significant REE mineralization belts in China, and includes the large Maoniuping and Daluxiang deposits and the minor Lizhuang deposit. The REE mineralization in these deposits is spatially and temporally associated with carbonatite–syenite complexes. Large proportional fluorites and REE minerals occurring as veins intrude Cretaceous granite and Oligocene syenite in Maoniuping, and Oligocene syenite and carbonatite in Lizhuang, and Miocene syenite in Daluxiang. Fluorite is also one of main gangue minerals in the world-class Bayan Obo REE deposit. We present a comparison of the trace element and isotopic compositions of fluorites from four REE deposits in the Panxi region and Bayan Obo. The fluorites from Maoniuping and Daluxiang are characterized by variable REE patterns, with either LREE enrichment or LREE depletion relative to MREE. Typically they have a larger range in La/Ho compared to Y/Ho ratios, and pronounced positive Y anomaly relative to chondrite-normalized REE patterns. Their REE distribution patterns are controlled by fluoride-complexes and the loss of separate LREE-rich minerals. Different Y/Ho (ca. 73 vs. 108) and initial Sr isotopic (ca. 0.7061 vs. 0.7077) ratios are observed between the fluorites from Maoniuping and Daluxiang, reflecting their different source compositions. This contrasts with the fluorites from Maoniuping and Lizhuang, which have similar initial Sr isotopes, and appear to be cogenetic. However, the Lizhuang fluorite shows a consistent depletion of LREE relative to MREE, as well as lower Y/Ho ratios and higher HREE content than that in Maoniuping. In this respect the Lizhuang fluorite may have precipitated from a late-stage fluid following abundant fluorite and REE mineral deposition in Maoniuping. Carbonate, more than fluoride complexing, appears to have a stronger control on REE fractionation in the Lizhuang fluorites. The fluorites from three deposits in Panxi region show uniform initial Sr and Nd isotopic compositions similar to their associated carbonatites, but differ from ore-veins found intruding wall rocks, e.g. granite in Maoniuping and syenite in Daluxiang. This is not consistent with a model for fluorite formation involving interaction of F-rich, carbonatite-exsoloved fluid with wall rocks. Instead, the fluorite in Panxi region may precipitate from a residual carbonthermal fluid, which was dominated by Ca, CO2 but also contained F, H2O and REE, and derived from the fractioned carbonatitic magma. Fluorite deposition produced a sharp drop in the activity of F−, which destabilized the REE fluoride complexes and caused deposition of REE minerals. In Bayan Obo, the fluorite typically has higher La/Ho than that in Panxi region and is characterized by a consistent LREE enrichment relative to MREE and negligible to positive Y anomalies. This is consistent with the compositional change of the hydrothermal fluids, which were infiltrated by external F-, LREE-rich fluids. The 87Sr/86Sr of Bayan Obo fluorite is relatively low radiogenic, and has a large range (0.7038–0.7065): similar characteristics to the carbonatite dykes found near the ore bodies. This supports a model for fluorite and REE mineral genesis involving the interaction of a carbonatite-derived fluid and the ore-hosted dolomitic marble.

A swarm of Late Triassic (220 Ma) carbonatite dykes is emplaced into the deformed southern margin of the North China block (NCB) at Lesser Qinling, discontinuously extending for about 10 km. The carbonatites are volumetrically minor, and their formation is related to collision between the South China block (SCB) and Qinling orogen, which led to the amalgamation of the NCB and SCB. The carbonatites are intruded into different Archean and Mesoproterozoic wall-rocks, but are characterized by remarkably similar isotopic compositions [(87Sr/86Sr)i = 0.7048–0.7057; ?Nd = ? 4.3 to ? 10.1; 207Pb/206Pb = 0.878–0.889 and 208Pb/206Pb = 2.136–2.160], which approach, and trend toward slightly less radiogenic Sr and Nd values than, the enriched mantle component EM1. Proterozoic oceanic crust recycled through deep mantle is interpreted to be the principal source of carbon for the Lesser Qinling carbonatites. In comparison with most other young carbonatites (< 200 Ma) emplaced in a rift setting, the Lesser Qinling suite contains appreciably lower ?Nd and higher 207Pb/206Pb and 208Pb/206Pb values, which suggest the presence of an isotopically distinct additional component in its mantle source. The Pb isotopic signature of these carbonatites is significantly distinct from that of the Precambrian rocks in the North China block, but is similar to that of basement rocks in the South Qinling. On the basis of the available isotopic, geophysical and tectonic constraints, we suggest that the southern margin of the North China block was underthrust by crustal material derived from the South Qinling during their collision. The underthrusting contributed to thickening of the lower crust beneath the North China block and its conversion to dense eclogite. This process culminated in brittle delamination of the eclogitized material into the mantle and its metasomatic reworking by carbonate-rich melts derived from the EM1-type recycled Proterozoic crust. Carbonate metasomatism could produce an enriched sub-continental lithospheric source capable of yielding a variety of magma types.

The western part of the Khan Bogd complex comprises (in order of emplacement): microcline-phyric granite, peralkaline aegirine-arfvedsonite granite (main intrusive phase) and aplite-pegmatite veins confined predominantly to the apical parts of the intrusion. These rocks are interpreted to represent products of extreme fractional crystallization what involved an increase in index of peralkalinity (from 1.0 in the porphyritic granite to 1.3 in the main phase to 2.5 in the pegmatite) and whole-rock Zr content (864 to 1130 to 16900 ppm). The hydrothermal stage involved replacement of the primary elpidite by late-stage Ca-rich elpidite or armstrongite, and then precipitation of minor gittinsite and abundant zircon. With the exception of zircon, all secondary zirconosilicates exhibit relative enrichment in light REE.

Carbonatites are known to contain the highest concentrations of rare-earth elements (REE) among all igneous rocks. The REE distribution of carbonatites is commonly believed to be controlled by that of the rock-forming Ca minerals (i.e., calcite, dolomite, and ankerite) and apatite because of their high modal content and tolerance for the substitution of Ca by light REE (LREE). Contrary to this conjecture, calcite from the Miaoya carbonatite (China), analyzed in situ by laser-ablation inductively-coupled-plasma mass-spectrometry, is characterized by low REE contents (100–260 ppm) and relatively flat chondrite-normalized REE distribution patterns [average (La/Yb)CN = 1.6]. The carbonatite contains abundant REE-rich minerals, including monazite and fluorapatite, both precipitated earlier than the REE-poor calcite, and REE-fluorocarbonates that postdated the calcite. Hydrothermal REE-bearing fluorite and barite veins are not observed at Miaoya. The textural and analytical evidence indicates that the initially high concentrations of REE and P in the carbonatitic magma facilitated early precipitation of REE-rich phosphates. Subsequent crystallization of REE-poor calcite led to enrichment of the residual liquid in REE, particularly LREE. This implies that REE are generally incompatible with respect to calcite and the calcite/melt partition coefficients for heavy REE (HREE) are significantly greater than those for LREE. Precipitation of REE-fluorocarbonates late in the evolutionary history resulted in depletion of the residual liquid in LREE, as manifested by the development of HREE-enriched late-stage calcite [(La/Yb)CN ≈ 0.7] in syenites associated with the carbonatite. The observed variations of REE distribution between calcite and whole rocks are interpreted to arise from multistage fractional crystallization (phosphates ⇒ calcite ⇒ REE-fluorocarbonates) from an initially REE-rich carbonatitic liquid.

The Qinling molybdenum belt is a prominent metallogenic structure in central China hosting several significant porphyry- and porphyry–skarn-type deposits. The Huanglongpu Mo deposit in the north-western part of the belt is unique in that it is associated with carbonatite dykes, rather than felsic magmatism. The carbonatites are composed largely of Sr–Mn-rich calcite and characterized by high concentrations of Sr and rare-earth elements (REE), and stable-isotope values indicative of a mantle source (δ13CPDB = − 6.7 ± 0.2‰ and δ18OSMOW = 8.2 ± 1.0‰). Molybdenite is associated with galena and REE minerals (parisite, bastnasite and monazite). Both molybdenite and galena are characterized by high Re contents (up to 0.4 and 0.2 wt.%, respectively) and Re/(Mo, Pb) ratios approaching the primitive-mantle values. In contrast to the rock-forming calcite, the REE minerals are enriched in light REE, whose relative proportion increases from parisite-(Ce) [average (La/Nd)n = 2.1] to bastnasite-(Ce) and monazite-(Ce) [average (La/Nd)n = 3.1, 4.6, respectively]. The whole-rock compositions are characterized by some of the highest Mo and heavy REE abundances reported for carbonatites to date: up to 1010 ppm Mo, 1130 ppm Y + Gd…Lu and (La/Yb)n = 1.2–2.7. The unusual trace-element geochemistry of the Huanglongpu rocks may ultimately reflect the composition of their mantle source, but their enrichment in Mo + Re was undoubtedly enhanced through preferential partitioning of these elements into a light REE–Pb–S-rich fluid derived from the carbonatitic magma modified by calcite fractionation. The present work shows that Mo can be retained, transported and deposited by carbonatitic fluids capable of generating economic Mo deposits.

Although cancer is one of the most dangerous and the second most lethal disease in the world, current therapy including surgery, chemotherapy, radiotherapy, etc., is highly insufficient not in the view of therapy success rate or the amount of side effects. Accordingly, procedures with better outcomes are highly desirable. Iron oxide nanoparticles (IONPs) present an innovative tool-ideal for innovation and implementation into practice. This review is focused on summarizing some well-known facts about pharmacokinetics, toxicity, and the types of IONPs, and furthermore, provides a survey of their use in cancer diagnosis and therapy.

Although carbonatites potentially contain a larger concentration of rare earth elements (REEs) than any rock type, the origin of the REE mineralization in the world's largest Bayan Obo carbonatite-related deposit is still disputed. In order to clarify the mechanism of REE mineralization, carbonatite samples from three large REE deposits in China, Daluxiang, Maoniuping and Bayan Obo were compared. The REE minerals in Daluxiang and Maoniuping carbonatites show constant light REE (LREE) enrichment (chondrite normalized (La/Nd)N ratios > 1), whereas those in Bayan Obo H8 dolomite marbles show variable (La/Nd)N ratios. The REE abundances and patterns of the REE minerals in Maoniuping carbonatites are similar to those in the barite, calcite and thread vein-hosted ores. The calcites in Daluxiang and Maoniuping carbonatites are characterized by enrichments of Pb, Sr and REEs, which is consistent with an igneous origin. They have similar REE contents and patterns to the corresponding bulk rocks, suggesting that these carbonatites are calcite-rich cumulates. During crystallization and accumulation of calcites, the REEs become enriched in carbonatite-expelled fluids because of the very low partition coefficients for these elements between carbonate minerals and melt. These fluids interact with the country rocks to produce fluorite-rich REE mineralization. The fluorites in Daluxiang and Maoniuping deposits are characterized by high Sr contents and REE patterns that vary from LREE enriched to LREE depleted. The former has relatively higher Sr and lower heavy REE (HREE) concentrations than those in Maoniuping, which is consistent with the differences found in carbonatites and calcites from the two locations. In addition, the high MnO, Sr and REE contents of dolomites in REE–Nb–Fe host H8 dolomite marble in Bayan Obo support the hypothesis that the rock is of igneous origin. In situ analyses show compositional differences between coarse- and fine-grained dolomites. The latter has higher Nb and LREEs, and lower FeO and 207Pb/206Pb and 208Pb/206Pb ratios. Our data confirm previous interpretations of the complex, multistage nature of REE and Nb mineralization at Bayan Obo, in which the ore is produced by reaction between carbonatite-derived fluids and the ore host dolomite marbles. This hypothesis is supported by the age of adjacent carbonatite dykes, which have the same age range as ore formation. A similar REE mineralization model is proposed for the Daluxiang and Maoniuping carbonatite deposits.

The microwave-assisted synthesis of goethite nanoparticles has been studied. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA) and Brunauer-Emmett-Teller (BET) method. Goethite rod-like nanoparticles have been successfully synthesized in 10 min of microwave treating at 100 degrees C. Particle size is in the range from 30 to 60 nm in width and from 200 to 350 nm in length. BET analysis indicated that the surface area of the product is 158.31 m(2)g(-1). The feasibility of Cr(VI) removal fromaqueous solution depends on the pH of the solution and contact time. The maximum adsorptionis reached at pH 4.0 and 540 min of contact time. The adsorption kinetics was analyzedby the pseudo-first-and second-order models and the results reveal that the adsorption process obeys the pseudo-second-order model. The adsorption data were fitted well with the Langmuir adsorption isotherm.

Clinoptilolite is a natural mineral with exceptional physical characteristics resulting from its special crystal structure, mainstreamed into a large zeolite group called heulandites. An overall view of the research related to the synthesis, modification and application of synthetic clinoptilolite is presented. A single phase of clinoptilolite can be hydrothermally synthesized for 1–10 days in an autoclave from various silica, alumina, and alkali sources with initial Si/Al ratio from 3.0 to 5.0 at a temperature range from 120 to 195 °C. Crystallization rate and crystallinity of clinoptilolite can be improved by seeding. The modification of clinoptilolite has received noticeable attention from the research community, since modified forms have specific properties and therefore their area of application has been broadening. This paper provides a review of the use of organic compounds such as quarter alkyl ammonium, polymer, amine and inorganic species used in the modification process, discusses the processes and mechanisms of clinoptilolite modification, and identifies research gaps and new perspectives.