Original Paper
Adaptation of an Analytical Procedure for Concurrent Determination of Np and Pu in clay samples
- Tobias Renz, Markus Plaschke, Francesca Quinto, Andreas Bauer, Markus Lagos, Heinrich Taubald, Horst Geckeis
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 183-189
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Np and Pu are two important actinides of concern for the safe long-term disposal of nuclear waste. Both actinides are, in addition, constituents of global nuclear fallout. Investigation of their environmental behavior requires ultra-sensitive analytical methods, but current methods for a concurrent determination in clay minerals are lacking. In the present study, a Pu isotope was investigated for use as a non-isotopic yield tracer for Np in extraction, purification, and mass spectrometric determination of Np and Pu isotopes in clay materials. Inductively coupled plasma mass spectrometry was used in this developmental study, but the method is intended for future ultra-trace analysis of global-fallout Np and Pu in clay-rich soil materials by the more sensitive accelerator mass spectrometry. Another field of application may be the investigation of diffusion patterns of actinides in compacted clay liners and potential host rocks for radioactive waste disposal. The analytical procedure includes the following steps: (1) extraction of Np and Pu from clay samples; (2) adjustment of Np and Pu to Np(IV) and Pu(III); (3) pre-concentration of Np and Pu by co-precipitation with iron hydroxide; (4) adjustment of Pu to Pu(IV); (5) extraction chromatographic separation of Pu and Np from iron and matrix elements; and (6) determination of Np and Pu by mass spectrometry. The analytical procedure was applied successfully to spiked montmorillonite and illite test portions of up to 1 g. High chemical yields near 90% were obtained for both Np and Pu. The suitability of Pu as a non-isotopic tracer for Np was indicated by Np/Pu chemical yield ratios close to unity. Accurate pH adjustment during the reductive co-precipitation and short processing times are vital to obtain high chemical yields and Np/Pu yield ratios close to unity.
The Interaction between Surfactants and Montmorillonite and its Influence on the Properties of Organo-Montmorillonite in Oil-Based Drilling FluIDS
- Guanzheng Zhuang, Zepeng Zhang, Shanmao Peng, Jiahua Gao, Francisco A. R. Pereira, Maguy Jaber
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 190-208
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The increasing demands for oil and gas and associated difficult drilling operations require oil-based drilling fluids that possess excellent rheological properties and thermal stability. The objective of the present work was to investigate the rheological properties and thermal stability of organo-montmorillonite (OMnt) modified with various surfactants and under various loading levels in oil-based drilling fluids, as revealed by the interaction between organic surfactants and montmorillonite. The influence of the structural arrangement of surfactants on the thermal stability of organo-montmorillonite (OMnt) in oil-based drilling fluids was also addressed. OMnt samples were prepared in aqueous solution using surfactants possessing either a single long alkyl chain two long alkyl chains. OMnt samples were characterized by X-ray diffraction, high-resolution transmission electron microscopy, thermal analysis, and X-ray photoelectron spectroscopy. Organic surfactants interacted with montmorillonite by electrostatic attraction. The arrangements of organic surfactants depended on the number of long alkyl chains and the geometrical shape of organic cations. In addition to the thermal stability of surfactants, intermolecular interaction also improved the thermal stability of OMnt/oil fluids. A tight paraffin-type bilayer arrangement contributed to the excellent rheological properties and thermal stability of OMnt/oil fluids. The deterioration of rheological properties of OMnt/oil fluids at temperatures up to 200°C was due mainly to the release of interlayer surfactants into the oil.
Effect of Mechanical Activation on the Pozzolanic Activity of Muscovite
- Geng Yao, Haoyu Zang, Junxiang Wang, Peng Wu, Jun Qiu, Xianjun Lyu
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 209-216
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In order to provide a theoretical foundation for the utilization of tailings as supplementary cementitious materials, the pozzolanic activity of muscovite—a typical mineral phase in tailings—before and after mechanical activation was investigated. In this study, significant pozzolanic activity of muscovite was obtained as a result of the structural and morphological changes that were induced by mechanical activation. The activated muscovite that was obtained after mechanical activation for 160 min satisfies the requirements for use as an active supplementary cementitious material, and the main characteristics of the pozzolana were as follows: median particle size (D50) of 11.7 μm, BET specific surface area of 28.82 m2 g−1, relative crystallinity of 14.99%, and pozzolanic activity index of 94.36%. Continuous grinding led to a gradual reduction in the relative crystallinity and an increase in the pozzolanic activity index due to the dehydroxylation reaction induced by mechanical activation, which occurred despite the fact that the specific surface area showed a decreasing trend when the grinding time was prolonged. Mechanically activated muscovite exhibited the capacity to react with calcium hydroxide to form calcium silicate hydrate, which is a typical characteristic of pozzolana. This experimental study provided a theoretical basis for evaluating the pozzolanic activity of muscovite using mechanical activation.
Iron Mineralogy and Magnetic Susceptibility of Soils Developed on Various Rocks in Western Iran
- Shamsollah Ayoubi, Vali Adman
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 217-227
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The characterization of magnetic minerals and the relationship of these minerals to the magnetic susceptibility of soils that have developed on various parent materials can provide valuable information to various disciplines, such as soil evolution and environmental science. The aim of the study reported here was to investigate variations in the magnetic susceptibility (χ) of soils in western Iran due to differences in lithology and to examine the relationship of χ to ferrimagnetic minerals. Eighty samples were collected from eight parent materials taken from both intact rocks and associated soils. The soil parent materials included a range of igneous and sedimentary rocks, such as ultrabasic rocks (Eocene), basalt (Eocene), andesite (Eocene), limestone (Permian), shale (Cretaceous), marl (Cretaceous), and the Qom formation (partially consolidated fine evaporative materials, early Miocene). The 80 samples were analyzed for χ using a dual-frequency magnetic sensor and for mineralogy using X-ray diffraction (XRD). The highest χ values were found in the ultrabasic rocks and associated soils, while the lowest χ values were observed in the limestone rocks and associated soils. The pedogenic processes significantly enhanced the χ values of soils developed on the sedimentary rocks due to the formation of ferrimagnetic minerals. In contrast, χ values decreased as a result of pedogenic processes in soils developed on igneous rocks due to the dilution effects of diamagnetic materials, such as halite, calcite, phyllosilicates, and organic matter. The significant positive correlation between the XRD peak intensity of the maghemite/magnetite particles and χ values confirmed that χ values in soils are largely controlled by the distribution and content of ferrimagnetic minerals. These results show that χ measurements can be used to quantify low concentrations of ferrimagnetic minerals in the soils of semiarid regions.
A New Kaolin Deposit in Western Africa: Mineralogical and Compositional Features of Kaolinite from Caluquembe (Angola)
- Esperança Tauler, Jingyao Xu, Marc Campeny, Sandra Amores, Joan Carles Melgarejo, Salvador Martinez, Antonio O. Gonçalves
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 228-243
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Large kaolin deposits developed by weathering on Precambrian granitic rocks have been discovered in the Caluquembe area, Huíla province, Angola. To determine accuracy of analysis and to evaluate the kaolinite grade, a full-profile Rietveld refinement by X-ray Powder Diffraction (XRPD) and Thermal Gravimetric Analysis (TGA) was used. Caluquembe kaolin is composed mainly of kaolinite (44–93 wt.%), quartz (0–23 wt.%), and feldspar (4–14 wt.%). The Aparicio-Galán-Ferrell index (AGFI), calculated by XRPD profile refinement, indicates low- and medium-defect kaolinite. Kaolinite particles show a platy habit and they stack together forming ‘booklets’ or radial aggregates; they also occur as small anhedral particles in a finer-grained mass. Muscovite-kaolinite intergrowths have also been found. Whole-rock chemical analysis included major, trace, and Rare Earth Elements (REE). Chondrite-normalized REE patterns show the same tendency for all samples, with a significant enrichment in Light Rare Earth Elements (LREE). Mineralogical and compositional features of the Caluquembe kaolin indicate that it is a suitable material for the manufacture of structural products, such as bricks, paving stones, and roofing tiles. In addition, the significant REE contents of the Caluquembe kaolin can be considered as a potential future target of mining exploration.
Preparation of a Novel Clay/Dye Composite and its Application in Contaminant Detection
- Limei Wu, Xuyuan Bao, Haoyu Zhong, Yuwei Pan, Guocheng Lv, Libing Liao
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 244-251
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Although fluorescence detection is a sensitive method in the field of pollutant analysis, its application is restricted due to the fluorescence shown by organic material being quenched after aggregation and to low photo-thermal stability. To address these issues, a novel mineral/dye composite material was prepared by intercalating a fluorescence molecule, Rhodamine (R6G), into the interlayer space of montmorillonite (Mnt). This composite material greatly enhanced the light stability and efficiency of R6G. After enhancement, the fluorescence lifetime of R6G-Mnt was eight times longer than originally and the luminous intensity was 20 times greater. Chromium at the mmol/L (mM) level can be detected by the naked eye when its enhanced fluorescent property is fabricated into a solid test paper, even though a fluorescence spectrophotometer should be used for detection at the 0.01 μmol/L level in the sensing range 0.01 μmol/L to 100 mmol/L. These results can provide new avenues as well as a theoretical and experimental foundation for the development of novel supramolecular luminescent material.