Microalgae for the Extraction and Separation of Rare Earths: An STXM Study of Ce, Gd, and P

Maxence Plouviez, Benoit Guieysse, Karla Wolmarans, Andrea Marie E. Matinong, Olivia Buwalda, Karina Thånell, Igor Beinik, J. R. Marius Tuyishime, Valerie Mitchell, Peter Kappen, David Flynn, Thierry Jauffrais and Richard G. Haverkamp*, 
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Abstract

Rare earth elements (lanthanides) are critical materials for many applications, particularly those involved in new energy. Extracting these elements economically from low-concentration sources may be challenging. This study investigates the interaction of Ce and Gd with microalgae that have been triggered to form phosphate-rich granules. Lanthanides usually occur in nature as phosphates, and therefore, we hypothesized that phosphate accumulation in microalgae may facilitate lanthanide sequestration. Synchrotron-based scanning transmission X-ray microspectroscopy (STXM) was used to map the distribution of Gd, Ce, and P in and around cells of Chlamydomonas reinhardtii. STXM provided X-ray absorption (XAS) spectra at the Gd M4,5-edge, the Ce M4,5-edge, and the P K-edge, supported by bulk X-ray absorption spectroscopy at another beamline, and elemental maps from scanning electron microscopy with energy-dispersive spectroscopy (SEM/EDS). Gd was associated with P in polyphosphate granules within C. reinhardtii and with P outside the cells. Ce was associated with P outside the microalgal cells but not with the P granules inside the cells. Gd and Ce were found to react with phosphate to form a distinct compound apparent in X-ray absorption near edge spectroscopy (XANES) of bulk samples. However, this compound is not found in the P granules that are coincident with Gd inside the alga. These differences in uptake by the microalga between Ce and Gd may suggest a selective extraction technique and could be generalized to other rare earth elements that are otherwise hard to separate.

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用于提取和分离稀土的微藻:对 Ce、Gd 和 P 的 STXM 研究
稀土元素(镧系元素)是许多应用领域,尤其是新能源领域的关键材料。从低浓度资源中经济地提取这些元素可能具有挑战性。本研究调查了铈和钆与微藻类的相互作用,微藻类被激发形成富含磷酸盐的颗粒。镧系元素在自然界中通常以磷酸盐的形式存在,因此,我们假设微藻中磷酸盐的积累可能会促进镧系元素的封存。我们利用同步辐射扫描透射 X 射线显微光谱(STXM)来绘制衣藻细胞内和细胞周围钆、铈和磷的分布图。STXM 提供了 Gd M4,5-边、Ce M4,5- 边和 P K-边的 X 射线吸收(XAS)光谱,并得到了另一条光束线的体 X 射线吸收光谱以及扫描电子显微镜与能量色散光谱(SEM/EDS)的元素图谱的支持。Gd 与 C. reinhardtii 细胞内聚磷酸盐颗粒中的 P 以及细胞外的 P 有关。铈与微藻细胞外的磷有关,但与细胞内的磷颗粒无关。研究发现,钆和铈与磷酸盐反应形成一种独特的化合物,在块状样品的 X 射线吸收近缘光谱(XANES)中显而易见。然而,在藻体内与 Gd 同时存在的 P 颗粒中却没有发现这种化合物。微藻对铈和钆吸收的这些差异可能暗示了一种选择性萃取技术,并可推广到其他难以分离的稀土元素。
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