1. Radium at Needle's Eye, Scotland, UK
- Author
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Kosmidis, Dimitris
- Subjects
540 ,Chemical Sciences not elsewhere classified ,radium ,radium analyses ,radium-226 ,gamma spectroscopy ,Soils ,XRD characterization ,EDXAFS ,Heavy Metal Levels ,Natural Organic Matter Samples ,Topsoil Type ,Mobility ,Sorption ,uranium-238 ,uranium-235 ,Sequential Extraction Method ,column experiments ,Liquid Scintillation Counter ,UV-vis spectroscopy ,loss on ignition (LOI) ,ICPMS ,ICPOES ,XRF analysis ,Soil texture analysis ,soil sampling ,SEM analyses ,bismuth-214 ,lead-214 ,Scotland Caledonian orogenesis ,Needle's Eye ,radium speciation - Abstract
Samples of soil have been taken from five different locations in Needle's Eye Scotland to establish the processes and conditions which govern the possible movement of radium through the natural environment at the site. The samples were analysed using gamma spectroscopy, powder X-ray diffraction (PXRD), loss on ignition, X-ray fluorescence (XRF), UV/visible spectroscopy, scanning electron microscopy (SEM), and ICP MS - OES to determine the quantity of radium at different areas in the site and examine whether the levels were associated with any particular organic and inorganic phase. Initial gamma spectroscopy measurements on samples taken from Needle's Eye highlighted some key challenges with the determination of radium by inference by using the measurement of the uranium series progenies, bismuth and lead. Equilibrium between 226Ra and the two progenies (²¹⁴Bi and ²¹⁴Pb) was not reached, despite long collection times due to loss of radon gas from the experimental container. Various containers including plastic and aluminium cans sealed with different substances (wax, tape and plastic encapsulation) were then trialled to eliminate radon loss and hence accurately determine the radium content as evidenced by equilibrium being reached. It was proven that aluminium canisters (sealed with wax, Teflon tape on the threads, Scotch tape and vacuum sealed plastic bags) produced the most reliable results since they minimised the radon loss when measuring radium indirectly. A method for measuring radium directly, including the determination of errors, which takes into account the overlap between uranium and radium emission lines in gamma spectroscopy, has been developed. The activity concentrations for the different samples collected from Needle's Eye (NE1 – NE5) varied significantly; ²²⁶Ra varied from 0.67x10² ± 0.05x10² to 26.67x10² ± 6.40x10² Bq kg⁻¹, ²¹⁴Pb varied from 0.25x10² ± 0.03x10² to 17.70x10² ± 2.00x10² Bq kg⁻¹ and ²¹⁴Bi varied from 1.63x10² ± 0.12x10² to 17.30x10² ± 0.70x10² Bq kg⁻¹. The average activity ratios of Ra/Pb and Ra/Bi were found to be 1.48 ± 0.15 and 1.84 ± 0.34 respectively and showed significant variance from the ratio expected at equilibrium without radon loss. Loss on ignition treatment (500 and 1000 °C) was performed at the five sites and varied significantly (3.2 – 39.1%). UV - Vis analysis of samples generated by creating equilibrated water from the samples and altering the pH, suggests that the natural organic matter present in the Needle's Eye soil samples is dominated by humin, followed by lesser amounts of fulvic and humic acids. Further investigation of the soil from Needle's Eye was conducted by characterisation of topsoil (NE4T) from the organic rich location of the site. Significant amounts of radium were found to be present in topsoil (~ 30x10³ Bq kg⁻¹). Loss on ignition treatment (500 and 1000 °C) on the topsoil recorded mass a loss of ~ 86%, and further CHN analysis reported a strong presence of carbon (~ 41%) suggesting that about half of the mass lost during loss on ignition experiments is associated with organic carbon and the rest is from carbonate and the breakdown of hydrated minerals. The relative high percentages for carbon, in topsoil, are not surprising when taking into account the natural origin of the samples and the background geology of the site which is dominated by the presence of limestone (CaCO₃), hornblende (Ca₂(Mg,Fe, Al)5(Al, Si)₈O₂₂(OH)₂), and granodiorite (rich in calcium). Sequential extractions were performed on topsoil and deeper soil from the organic rich locality and showed that radium at Needle's Eye is not associated with a single fraction. Approximatelly 80% (combined) of the radium was split between 4 fractions with the carbonate fraction (i.e. calcite (CaCO₃) and dolomite (CaMg(CO₃))), with iron and manganese oxides (i.e. ferrihydrite ((Fe³⁺)₂O₃·0.5H₂O), goethite (FeO(OH)), and hematite (Fe₂O₃)), with the organic fraction (i.e. humin), and with the residual fraction (i.e. silicates, feldspars, and sulfates). PXRD analysis of the bulk soil phases was only successful in identifying quartz (SiO₂), muscovite (KAl₂(AlSi₃O₁₀)(F,OH)₂) and chlorite (Mg,Al)₆(Si,Al)₄O₁₀(OH)₈) phases as well as poorly crystalline feldspar phases as inorganic components of the soil samples taken from Needle's Eye due to the large proportion of organic matter in the soil. Using Loss on Ignition at 500°C to remove the organic phases but retain the inorganics showed the presence of carbonate mineral phases, such as, calcite (CaCO₃) and sulfate containing phases such as anhydrite (CaSO₄); as expected since limestone is present in the geology of Needle's eye site together with gypsum (CaSO₄.2H₂O and baryte (BaSO₄). Furthermore, PXRD analysis of the topsoil sample after heating at 1000°C to crystallise out the poorly crystalline iron phases evidenced by sequential extraction indicated prominent phases are anhydrite, gehlenite (CaSi₂Al₂O₇), quartz (SiO₂) and magnesioferrite (MgFe₂O₄). PXRD analysis supported by XRF elemental analysis, which showed elevated concentrations for calcium, may also suggest the presence of anhydrite (CaSO₄), as well as calcite (CaCO₃) after the sequential extraction of the carbonate fraction. The sorption experiments that were performed using topsoil under three different conditions for the binary experiments (i.e. radium spiked equilibrated water with topsoil, radium spiked demineralised water with topsoil, and radium spiked demineralised water with prewashed topsoil). The distribution ratios for radium were reported to vary between 158.3- and 180.1- mL g⁻¹ suggesting that radium is not mobile under these conditions. Radium mobility was conducted by using column experiments in an effort to duplicate the environmental conditions of the Needle's Eye site. Therefore, topsoil was used in a column and radium spiked equilibrated water was passed through the column. In the analysis of the effluent fractions coming out of the column, radium was not detected and therefore it was concluded that radium is not mobile under these conditions.
- Published
- 2019
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