X-ray diffraction (XRD) patterns of four kinds of sieved samples after adsorption of metals are shown in Fig. 11. Similar to the XRD patterns before adsorption of metals, aragonite and calcite were found as the main crystal structure in (a): Ground original sample and (b): Heat — treatment (480°C, 6h) sample, respectively. However, the decrease of peak and increase of noise were also observed in both patterns, particularly in the ground original material as shown in Fig. 11(a). Bottcher [37] pointed out that the natural powdered aragonite was transformed to mixed rhombohedral carbonates by the reaction with (Ca, Mg)-chloride solutions. Therefore, there is the possibility that the transformation of aragonite occurred by the reaction with lanthanides in our experiment.

Moreover, according to XRD analysis, the main crystal structure of (c): "Heat-treatment (950°C) sample" was transformed from calcium oxide (CaO) to the mixture of calcium hydroxide (Ca(OH)2) and calcite (CaCO3) after exposing metals; and that of (d): "Heat — treatment (950°C) and water added sample" was transformed from calcium hydroxide(Ca(OH)2) to calcite (CaCO3) after adsorption of metals. These changes may be due to the reaction with water or carbon dioxide in atmosphere.

SEM pictures of four kinds of shell biomass after adsorption of metals are shown in Fig. 12. By comparing SEM pictures in Fig. 8 with that in Fig. 12, it is found that the morphology of sample (a) and (b) has hardly changed even after exposing metals. From this observation, these sieved samples should be predicted to withstand the repeated use; and hence it can be a good adsorbent.

In contrast to sample (a), clear crystal structure (sizes are mostly 0.25-2.0pm) was observed in sample (b) even after adsorption of metal. In case of Cd conducted by Kohler et al. [38], the difference of procedure for reaction with metals between aragonite and calcite was suggested. According to their work, the precipitation of several distinct types of crystals was observed after exposing metals in the case of aragonite. Then, it is anticipated that similar phenomenon were occurred by adsorption of lanthanides in case of our samples. On the

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(d)

Figure 11. X-ray diffraction (XRD) patterns of Buccinum tenussimum shell biomass after adsorption of metals. (a) ground original sample, (b) heat-treatment (480°C) sample, (c) heat-treatment (950°C) sample, (d) heat-treatment (950°C) and water added sample

(d)

other hand, the surface of sample (c) and (d) after exposing metals have changed largely compared to that before adsorption of metals (Fig. 8). This is in good accord with the results of XRD patterns. Particularly, remarkable transformation was observed in the morphology of sample (d). The reaction of sample (d) with metal is supposed to proceed rapidly.