The role of carbonate-fluoride melt immiscibility in shallow REE deposit evolution

The Lugiin Gol nepheline syenite intrusion, Mongolia, hosts a range of carbonatite dikes mineralized in rare-earth elements (REE). Both carbonatites and nepheline syenite-fluoritecalcite veinlets are host to a previously unreported macroscale texture involving pseudographic 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 calcitefluorite 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 carbonatefluoride 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

Sunflower Plants as Bioindicators of Environmental Pollution with Lead (II) Ions

In this study, the influence of lead (II) ions on sunflower growth and biochemistry was investigated from various points of view. Sunflower plants were treated with 0, 10, 50, 100 and/or 500 μM Pb-EDTA for eight days. We observed alterations in growth in all experimental groups compared with non-treated control plants. Further we determined total content of proteins by a Bradford protein assay. By the eighth day of the experiment, total protein contents in all treated plants were much lower compared to control. Particularly noticeable was the loss of approx. 8 μg/mL or 15 μg/mL in shoots or roots of plants treated with 100 mM Pb-EDTA. We also focused our attention on the activity of alanine transaminase (ALT), aspartate transaminase (AST) and urease. Activity of the enzymes increased with increasing length of the treatment and applied concentration of lead (II) ions. This increase corresponds well with a higher metabolic activity of treated plants. Contents of cysteine, reduced glutathione (GSH), oxidized glutathione (GSSG) and phytochelatin 2 (PC2) were determined by high performance liquid chromatography with electrochemical detection. Cysteine content declined in roots of plants with the increasing time of treatment of plants with Pb-EDTA and the concentration of toxic substance. Moreover, we observed ten times higher content of cysteine in roots in comparison with shoots. The observed reduction of cysteine content probably relates with its utilization for biosynthesis of GSH and phytochelatins, because the content of GSH and PC2 was similar in roots and shoots and increased with increased treatment time and concentration of Pb-EDTA. Moreover, we observed oxidative stress caused by Pb-EDTA in roots where the GSSG/GSH ratio was about 0.66. In shoots, the oxidative stress was less distinctive, with a GSSG/GSH ratio 0.14. We also estimated the rate of phytochelatin biosynthesis from the slope of linear equations plotted with data measured in the particular experimental group. The highest rate was detected in roots treated with 100 μM of Pb-EDTA. To determine heavy metal ions many analytical instruments can be used, however, most of them are only able to quantify total content of the metals. This problem can be overcome using laser induced breakdown spectroscopy, because it is able to provide a high spatial-distribution of metal ions in different types of materials, including plant tissues. Data obtained were used to assemble 3D maps of Pb and Mg distribution. Distribution of these elements is concentrated around main vascular bundle of leaf, which means around midrib

The role of carbonate-fluoride melt immiscibility in shallow REE deposit evolution

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, Mongoli

Biochar-Assisted Phytostabilization for Potentially Toxic Element Immobilization

In response to the growing threat to the quality of the soil environment, new technologies are being developed to protect and remediate contaminated sites. A new approach, namely, assisted phytostabilization, has been used in areas contaminated with high levels of potentially toxic elements (PTEs), using various soil additives. This paper determined the effectiveness of biochar-assisted phytostabilization using Dactylis glomerata L. of soil contaminated with high concentrations of the selected PTEs (in mg/kg soil): Cu (780 ± 144), Cd (25.9 ± 2.5), Pb (13,540 ± 669) and Zn (8433 ± 1376). The content of the selected PTEs in the roots and above-ground parts of the tested grass, and in the soil, was determined by atomic absorption spectrometry (AAS). The addition of biochar to the contaminated soil led to an increase in plant biomass and caused an increase in soil pH values. Concentrations of Cu, Cd, Pb and Zn were higher in the roots than in the above-ground parts of Dactylis glomerata L. The application of biochar significantly reduced the total content of PTEs in the soil after finishing the phytostabilization experiment, as well as reducing the content of bioavailable forms extracted from the soil using CaCl2 solution, which was clearly visible with respect to Cd and Pb. It is concluded that the use of biochar in supporting the processes of assisted phytostabilization of soils contaminated with PTEs is justified

Biochar-Assisted Phytostabilization for Potentially Toxic Element Immobilization

In response to the growing threat to the quality of the soil environment, new technologies are being developed to protect and remediate contaminated sites. A new approach, namely, assisted phytostabilization, has been used in areas contaminated with high levels of potentially toxic elements (PTEs), using various soil additives. This paper determined the effectiveness of biochar-assisted phytostabilization using Dactylis glomerata L. of soil contaminated with high concentrations of the selected PTEs (in mg/kg soil): Cu (780 ± 144), Cd (25.9 ± 2.5), Pb (13,540 ± 669) and Zn (8433 ± 1376). The content of the selected PTEs in the roots and above-ground parts of the tested grass, and in the soil, was determined by atomic absorption spectrometry (AAS). The addition of biochar to the contaminated soil led to an increase in plant biomass and caused an increase in soil pH values. Concentrations of Cu, Cd, Pb and Zn were higher in the roots than in the above-ground parts of Dactylis glomerata L. The application of biochar significantly reduced the total content of PTEs in the soil after finishing the phytostabilization experiment, as well as reducing the content of bioavailable forms extracted from the soil using CaCl2 solution, which was clearly visible with respect to Cd and Pb. It is concluded that the use of biochar in supporting the processes of assisted phytostabilization of soils contaminated with PTEs is justified

Multi-instrumental Analysis of Tissues of Sunflower Plants Treated with Silver(I) Ions – Plants as Bioindicators of Environmental Pollution

The aim of this work is to investigate sunflower plants response on stressinduced by silver(I) ions. The sunflower plants were exposed to silver(I) ions (0, 0.1, 0.5,and 1 mM) for 96 h. Primarily we aimed our attention to observation of basic physiologicalparameters. We found that the treated plants embodied growth depression, coloured changes and lack root hairs. Using of autofluorescence of anatomical structures, such aslignified cell walls, it was possible to determine the changes of important shoot and rootstructures, mainly vascular bungles and development of secondary thickening. Thedifferences in vascular bundles organisation, parenchymatic pith development in the rootcentre and the reduction of phloem part of vascular bundles were well observable.Moreover with increasing silver(I) ions concentration the vitality of rhizodermal cellsdeclined; rhizodermal cells early necrosed and were replaced by the cells of exodermis.Further we employed laser induced breakdown spectroscopy for determination of spatialdistribution of silver(I) ions in tissues of the treated plants. The Ag is accumulated mainlyin near-root part of the sample. Moreover basic biochemical indicators of environmentalstress were investigated. The total content of proteins expressively decreased withincreasing silver(I) ions dose and the time of the treatment. As we compare the resultsobtained by protein analysis – the total protein contents in shoot as well as root parts – wecan assume on the transport of the proteins from the roots to shoots. This phenomenon canbe related with the cascade of processes connecting with photosynthesis. The secondbiochemical parameter, which we investigated, was urease activity. If we compared theactivity in treated plants with control, we found out that presence of silver(I) ions markedlyenhanced the activity of urease at all applied doses of this toxic metal. Finally we studiedthe effect of silver(I) ions on activity of urease in in vitro conditions