蓝藻对纳米矿物中稀土元素的分馏作用

doi:10.11867/j.issn.1001-8166.2025.044

表生环境中广泛存在纳米铁（氢）氧化物和磷酸盐矿物，这些物质相对磷（P）和稀土元素具有显著的固定作用。以含磷和稀土元素的水铁矿和磷灰石为磷源，采用透析方法（阻隔细胞与矿物），探究弱碱性和高CO $3 2 -$ 浓度条件下蓝藻（铜绿微囊藻，Microcystis aeruginosa）对纳米矿物结合态磷的利用及其对稀土元素的分馏作用。结果表明铜绿微囊藻可以较低的效率利用纳米矿物结合态磷，而溶解态和纳米颗粒结合态稀土元素均对铜绿微囊藻产生一定程度的毒害作用。稀土元素实验中，经过17 d的培养后，所有实验溶液均富重稀土；对于藻细胞及胞外多聚物，除高浓度溶解态稀土元素实验（富轻稀土）和水铁矿+透析实验（富重稀土）中出现稀土元素分馏外，其余实验中稀土元素均无分馏；丝状胞外多聚物富中稀土，尤其富含钐（Sm）、铕（Eu）和钆（Gd），而次生钙磷酸盐和铁（氢）氧化物则富集中—重稀土。研究认为，弱碱性条件下菌体及胞外多聚物对REE³⁺的选择性吸附导致溶液中总是富重稀土；溶液中稀土元素与阴离子（尤其是CO $3 2 -$ ）比值大时菌体和胞外多聚物中富轻稀土；稀土元素来源于矿物时，菌体及胞外多聚物中稀土元素分馏不明显；胞外多聚物选择性络合矿物中的稀土元素可能导致菌体及胞外多聚物中富重稀土；胞外多聚物及次生物相选择性富集中—重稀土可能具有潜在的环境指示意义。

关键词: 蓝藻, 纳米矿物, 磷, 稀土元素, 分馏

Nanosized iron (hydr)oxides and phosphate minerals are widely distributed in supergene environments and exhibit significant sequestration effects for phosphorus (P) and Rare Earth Element (REE). Although previous studies have found that both forms of P can be utilized by microorganisms, the mechanism by which microbial activity constrains the geochemical behavior of mineral-bound REEs during P utilization has received little attention. This study investigated the utilization of Nano-mineral bound P by Microcystis aeruginosa and the associated REEs fractionation under weakly alkaline and high CO $3 2 -$ conditions, using ferrihydrite (Fh) and apatite (Ap) loaded with P and REEs as P sources through dialysis methods (isolating cells from minerals). The results demonstrated that M. aeruginosa utilized nano-mineral-bound P with low efficiency, while both dissolved and nano-mineral-bound REEs exhibited moderate toxicity to the cyanobacterium. In the REE experiments, all the solutions were enriched in Heavy REEs (HREEs) after 17 d of cultivation. For algal cells and Extracellular Polymeric Substances (EPS), REE fractionation was observed only in experiments with high dissolved REE concentrations (enriched in LREEs and LREEs) and ferrihydrite + dialysis (enriched in HREEs). Filamentous EPS preferentially accumulated middle REEs (MREEs, particularly Sm, Eu, and Gd), whereas secondary calcium phosphates and iron (hydr)oxides sequestered MREEs-HREEs. It is considered that: ① Selective adsorption of REE³⁺ under weak alkaline conditions by Cells and EPS (C&E) consistently enriches HREEs in solutions; ② Cells and EPS enrichment in LREEs occurs when the REE/anion (especially CO $3 2 -$ ) ratio in solution is elevated; ③ No REE fractionation in cells and EPS when REEs originate from mineral phases; ④ EPS-mediated selective REE complexation from minerals may drive HREE enrichment in cells and EPS; ⑤ Preferential accumulation of MREEs-HREEs in EPS and secondary solid phases may underlie the positive anomalies of these elements in eutrophic waters. Thus, anomalies in MREEs (e.g., Eu) may serve as effective proxies for assessing the degree of aquatic eutrophication.

Key words: Cyanobacterium, Nanomineral, Phosphorus, Rare Earth Element, Fractionation.

中图分类号:

P574
595

表1 纳米磷灰石和水铁矿中稀土元素含量 (g/kg)

Table 1 Rare Earth Element （REE） content of apatite and ferrihydrite

矿物	La	Ce	Pr	Nd	Sm	Eu	Gd
纳米磷灰石	1.737	1.693	1.616	1.531	1.478	1.634	1.666
水铁矿	1.855	1.831	1.753	1.813	1.615	1.769	1.802
矿物	Tb	Dy	Ho	Er	Tm	Yb	Lu
纳米磷灰石	1.607	1.632	1.579	1.640	1.601	1.649	1.604
水铁矿	1.742	1.775	1.731	1.795	1.756	1.813	1.752

表1 纳米磷灰石和水铁矿中稀土元素含量 (g/kg)

Table 1 Rare Earth Element （REE） content of apatite and ferrihydrite

矿物	La	Ce	Pr	Nd	Sm	Eu	Gd
纳米磷灰石	1.737	1.693	1.616	1.531	1.478	1.634	1.666
水铁矿	1.855	1.831	1.753	1.813	1.615	1.769	1.802
矿物	Tb	Dy	Ho	Er	Tm	Yb	Lu
纳米磷灰石	1.607	1.632	1.579	1.640	1.601	1.649	1.604
水铁矿	1.742	1.775	1.731	1.795	1.756	1.813	1.752

图1 无稀土元素实验培养5 d后的 Microcystis aeruginosa 荧光图像

Fig. 1 Fluorescent images of Microcystis aeruginosa after 5 d of culture in experiments without Rare Earth Element （REE）

图2 无稀土元素实验培养20 d后的 Microcystis aeruginosa 荧光图像

Fig. 2 Fluorescent images of Microcystis aeruginosa after 20 d of culture in experiments without Rare Earth Element （REE）

图3 稀土元素实验中 Microcystis aeruginosa 生长曲线

Fig. 3 Growth curves of Microcystis aeruginosa in Rare Earth Element （REE） experiments

图4 稀土元素实验中 ¹³C和 ³¹P固体核磁共振谱

Fig. 4 Solid-state Nuclear Magnetic Resonance （ssNMR） results of ¹³C and ³¹P in Rare Earth Element （REE） experiments

图5 稀土元素实验中溶液和细胞中稀土元素浓度

Fig. 5 Rare Earth Element （REE） concentration in solution and cells in REE experiments

附图1 （http：//www.adearth.ac.cn/fileup/1001-8166/SUPPL/supplFile_art_20250716112823.jpg）

图6 接触实验中细胞高角环形暗场像图和元素微区分布图红色： P；绿色：Ca；蓝色：Fe。

Fig. 6 High-Angle Annular Dark Field （HAADF） images and element distribution maps of cells in contact experiments Red： P； Green： Ca； Blue： Fe.

附图2 （http：//www.adearth.ac.cn/fileup/1001-8166/SUPPL/supplFile_art_20250716112832.jpg）

图7 透析实验中细胞高角环形暗场像图和元素微区分布图红色： P或Sm；绿色：Ca；粉红色：Fe或Ho；浅蓝色：Sm；黄色：Tb；Ca/P分布图中的黄色为红色与绿色叠加后的颜色。

Fig. 7 High-Angle Annular Dark Field （HAADF） images and element distribution maps of cells in dialysis experiments Red： P or Sm； Green： Ca； Pink： Fe or Ho； aquamarine： Sm； yellow： Tb； yellow color in Ca/P distribution maps is derived from the stacking of red and green colors.

附图3 （http：//www.adearth.ac.cn/fileup/1001-8166/SUPPL/supplFile_art_20250716112841.jpg）

附图4 （http：//www.adearth.ac.cn/fileup/1001-8166/SUPPL/supplFile_art_20250716112914.jpg）

附图5 （http：//www.adearth.ac.cn/fileup/1001-8166/SUPPL/supplFile_art_20250716112923.jpg）

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Rare Earth Fractionation from Nanominerals by Cyanobacteria

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Rare Earth Fractionation from Nanominerals by Cyanobacteria