Insight into the adsorption of europium(III) on muscovite and phlogopite: Effects of pH, electrolytes, humic substances and mica structures.

Europium(III), i.e., Eu(III), is chemically analogous to the trivalent lanthanides (Ln) and actinides (An). A good understanding of the adsorption behaviour of Eu(III) on mica group minerals is critical to the safety evaluation of the radioactive contamination. Nevertheless, the structural complexity of micaceous minerals makes it difficult to draw a consistent conclusion in the study of Eu(III) migration. In this work, we contrastively studied Eu(III) adsorption on dioctahedral muscovite and trioctahedral phlogopite as functions of pH, ionic strength, background electrolytes, interaction sequence, and fulvic acid (FA). Batch experiments showed that Eu(III) adsorption on both micas was strongly dependent on pH but quite independent on ionic strength that is determined by Na+. Planar sites are available on both muscovite and phlogopite while interlayer sites only on phlogopite under Na+ and Ca2+ electrolytes (not for K+ and Cs+). An interlayer expansion of phlogopite, as indicated by a newly appeared diffraction peak at ~6° 2-theta, occurred along with Eu(III) adsorption, which was also confirmed by transmission electron microscopy. Furthermore, the initial Eu(III) concentrations, the concentration ratios between Eu(III) and Cs+, and the reaction sequences of Eu(III)-electrolytes-FA affected both the adsorption behaviour of Eu(III) and reversely the structural alteration of phlogopite. The sequential extraction showed that the adsorbed Eu(III) was mainly in the ion-exchangeable form while the addition of FA could increase the portion of coordinative species. The currently proposed Eu(III) adsorption mechanism can shed new light on predicting the migration of Ln/An(III) at the mica-rich solid-liquid interface on a molecular scale.

Comparative study of strontium adsorption on muscovite, biotite and phlogopite.

Micaceous minerals are the natural materials that can block radioactive strontium (Sr) released in the environment, and their adsorption capacity and mechanism are highly divergent owing to the different properties of micas. In this work, we comparatively studied the adsorption of Sr(II) on three typical micas, muscovite, biotite and phlogopite. The effects of pH, contact time, ionic strength, and background electrolyte were evaluated. It was found that phlogopite and muscovite had the largest solid-liquid distribution coefficient (Kd) for a reaction time of 48 h under acidic and alkaline conditions, respectively. Under alkaline conditions, as the reaction time increased to 44 days, phlogopite and muscovite showed the highest and lowest Kd, respectively. The Kd for Sr(II) adsorption on biotite and phlogopite increased with increasing pH but decreased with increasing pH for muscovite. X-ray diffraction analysis revealed that the interlayer weathering of phlogopite (a new diffraction peak appeared at 2-theta of ~6.1°) occurred along with the adsorption of Sr(II) below pH 9.0 under 0.01 mol/L NaCl. Furthermore, the adsorption of Sr(II) was significantly inhibited in the presence of 10-5 and 10-2 mol/L Cs+, resulting in similar adsorption capacity for phlogopite and muscovite at pH ~4.1. Consequently, the difference in Sr(II) adsorption on muscovite, biotite and phlogopite mainly came from the synergistic process of adsorption and weathering, which induced the differences in availability of interlayer sites among micas over a certain time.