Interface Evolution and Multi-Process Coupling Mechanisms of Yttrium Recovery from Acid Mine Drainage by Limestone Cores Mediated by Iron and Manganese
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摘要: 文章以天然灰岩岩芯为研究对象，结合动态流动实验、BET、XRD、XPS表征及Phreeqc地球化学模拟，系统研究了酸性矿山废水（AMD）中稀土元素钇（Y(III)）在灰岩体系中的回收行为及作用机制，以及废水中赋存的Fe、Mn等金属元素对回收过程的影响机制。结果表明，Fe和Mn的参与未改变方解石晶体结构，但显著调控了材料表面性质，其中Fe的参与显著提高了比表面积并引入高密度Fe-OH活性位点，增强了体系对钇的富集与固定能力，在拟定吸附实验的前100 h出水钇浓度几乎为0。此外，Mn同样对灰岩表面性质及Y的去除行为产生了一定影响，表明Mn参与了界面反应过程并可能改变了表面活性位点分布。相较于含Fe体系，Mn对Y去除性能的影响相对较弱，因此本文主要针对Fe介导的界面作用进行了进一步讨论。Phreeqc模拟表明，方解石溶解导致体系pH升高至9.2并促进钇向稳定碳酸络合物转化，回收过程受矿物溶解–溶液络合–表面络合多过程耦合控制。在Fe参与条件下，钇在灰岩表面的固定稳定性显著提高，出水浓度波动减小，体系回收效率得到增强。研究结果表明，灰岩在Fe参与条件下具有一定的稀土资源化回收潜力，为酸性矿山废水中稀土元素的资源化利用提供了实验依据和理论支持。本研究创新性地揭示了Fe在灰岩表面形成的铁氧化物包覆层由传统钝化层向活性吸附界面层的转变机制，阐明了钇回收过程中由方解石溶解，铁氧化物界面重构以及表面络合构成的多过程耦合控制机制，构建了实验表征与Phreeqc模拟相结合的界面反应分析方法，为AMD中稀土元素高效资源化回收提供了新的认识。
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关键词:
- 稀土元素 /
- 岩芯 /
- 酸性矿山废水 /
- 资源化利用 /
- 表面络合模型(SCM)
Abstract: Rare earth elements (REEs) are indispensable strategic resources widely used in advanced technologies, including renewable energy systems, electronic devices, catalysts, and high-performance magnetic materials. As global demand for REEs continues to increase, the development of alternative and sustainable resource recovery technologies has become increasingly important. Acid mine drainage (AMD), a common by-product of mining activities, often contains elevated concentrations of dissolved rare earth elements and therefore represents a potentially valuable secondary resource. Among REEs, yttrium (Y) is commonly regarded as a representative heavy rare earth element because of its similar ionic radius, coordination behavior, and geochemical characteristics. Efficient recovery of yttrium from AMD can simultaneously reduce environmental risks and enhance resource utilization efficiency. Although a variety of technologies, including chemical precipitation, solvent extraction, ion exchange, membrane separation, and biosorption, have been applied to recover REEs from aqueous systems, these methods often suffer from high operational costs, complex procedures, or limited applicability under acidic conditions. Limestone, which mainly consists of calcite (CaCO3), is an inexpensive and widely available material capable of neutralizing acidity and interacting with dissolved metal ions. Previous studies have demonstrated that rare earth elements can be adsorbed onto carbonate minerals; however, the influence of coexisting metals such as iron (Fe) and manganese (Mn) on interfacial evolution and yttrium immobilization mechanisms remains poorly understood. In particular, the coupled effects of mineral dissolution, metal precipitation, aqueous complexation, and surface complexation have not been systematically investigated.In this study, natural limestone cores were employed as reactive media to investigate the recovery behavior of Y(III) from simulated AMD systems. Dynamic flow-through adsorption experiments were conducted to evaluate yttrium removal performance under continuous-flow conditions. Surface and mineralogical changes were characterized using Brunauer-Emmett-Teller (BET) surface area analysis, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Furthermore, PHREEQC geochemical simulations combined with a surface complexation model (SCM) were used to quantitatively analyze yttrium speciation, mineral-water interactions, and adsorption mechanisms. The results demonstrated that neither Fe nor Mn altered the crystal structure of calcite. XRD analyses showed that all samples remained dominated by calcite after treatment. However, significant differences in surface properties were observed. BET measurements revealed that Fe treatment increased the specific surface area of limestone from 13.99 to 24.36 m2·g−1, representing an increase of approximately 74%, whereas Mn treatment produced only a modest increase. XPS spectra confirmed the successful incorporation of Fe and Mn onto the limestone surface and indicated the formation of additional oxygen-containing functional groups. These findings suggest that Fe and Mn were primarily deposited as amorphous or poorly crystalline hydroxide phases rather than forming new crystalline minerals. Dynamic adsorption experiments showed that Fe substantially enhanced yttrium recovery performance. Under Fe-mediated conditions, the concentration of yttrium in the effluent remained nearly zero during the first 100h of operation, indicating extremely strong initial retention and delayed breakthrough behavior. The recovery efficiency exceeded 99% under optimized conditions. In contrast, Mn also improved yttrium removal but exhibited significantly weaker enhancement compared with Fe. These observations indicate that iron plays a dominant role in regulating yttrium immobilization at the mineral-water interface. PHREEQC simulations revealed that calcite dissolution strongly influenced system geochemistry. The initial acidic solution (pH 4.0) evolved toward alkaline conditions (approximately pH 9.2) as calcite dissolved and consumed hydrogen ions. This process released carbonate species into solution and promoted the formation of stable yttrium-carbonate complexes. Speciation calculations indicated that carbonate complexation became the dominant control on dissolved yttrium distribution after reaction. Nevertheless, surface adsorption remained an important mechanism for yttrium immobilization. When Fe was incorporated into the system, additional Fe-OH surface sites were introduced through the formation of hydrous ferric oxide-like coatings. Surface complexation modeling demonstrated that yttrium could form stable inner-sphere complexes with these Fe-OH groups. Compared with adsorption on calcite surfaces, Fe-mediated adsorption exhibited stronger binding strength and greater resistance to competitive effects from Ca2+ and carbonate ligands. Consequently, the presence of iron significantly enhanced yttrium fixation stability and reduced fluctuations in effluent concentration during long-term operation. A key finding of this study is that the iron-rich coating traditionally regarded as a passivating layer does not merely inhibit calcite dissolution. Instead, it evolves into a highly reactive interfacial layer that provides abundant adsorption sites for yttrium. This transformation fundamentally changes the role of iron precipitates in AMD treatment systems. The recovery process is controlled by a multi-process coupling mechanism involving calcite dissolution, pH regulation, iron hydroxide precipitation, aqueous carbonate complexation, and surface complexation reactions. These processes collectively determine the migration, enrichment, and stabilization of yttrium within the limestone system. Overall, this study provides new insights into the interfacial evolution and recovery mechanisms of yttrium in limestone-based AMD treatment systems. The results demonstrate that iron-mediated limestone possesses considerable potential for rare earth resource recovery and highlight the importance of reactive iron oxide interfaces in controlling yttrium behavior. The integrated experimental-modeling framework developed in this work offers a useful approach for understanding complex mineral-water interactions and provides a theoretical basis for the sustainable recovery of rare earth elements from acid mine drainage.-
Key words:
- REE /
- limestone core /
- AMD /
- resource utilization /
- surface complexation model (SCM)
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图 2 实验装置示意图
（1.实验水溶液储存箱，2.进水管，3.柱塞泵，4.压力表，5.流量计，6.致密岩体反应池，7.致密岩体岩样，8.氟橡胶套管，9.高压手动泵，10.连接口，11.出水管，12.收集装置。）
Figure 2. Schematic diagram of the experimental apparatus
(1. Experimental aqueous solution storage tank, 2. Inlet pipe, 3. Plunger pump, 4. Pressure gauge, 5. Flow meter, 6. Dense rock reaction cell,7. Dense rock sample, 8. Fluororubber sleeve, 9. High-pressure manual pump, 10. Connector, 11. Outlet pipe, 12. Collection device.)
图 8 反应时间对氯化铁浸泡岩芯回收率的影响
Figure 8. Effect of Reaction Time on Recovery Efficiency of Ferric Chloride−Soaked Core
表 1 岩芯浸泡条件
Table 1. Core immersion conditions
实验条件 数值 浸泡液浓度 20 μmol∙L−1 岩芯浸泡时间 24 h 岩芯烘干温度 130 ℃ 岩芯烘干时间 8 h 
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表 2 岩芯比表面积
Table 2. Specific surface area of core samples
原岩芯 铁盐浸泡岩芯 锰盐浸泡岩芯 比表面积/（m2∙g−1） 13.9936 24.3644 16.8336 增幅百分比 − 74% 21%
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表 3 氯化铁用量对回收率的影响
Table 3. Effect of ferric chloride dosage on recovery efficiency
用量/g 0.01 0.02 0.04 0.08 0.16 回收率/% 89.3764 93.0810 95.9958 99.7197 99.8191
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表 4 反应时间对回收率的影响
Table 4. Effect of reaction time on recovery efficiency
时间/h 2 4 6 12 24 48 72 回收率/% 90.3514 93.8677 95.9958 99.2378 99.2687 99.3465 99.5359
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表 5 反应后吸附状态分布
Table 5. Distribution of adsorption states after reaction
表面物种 mol 占比 Hfo_sO− 3.675e-6 61.2% Hfo_sOHCa2+ 1.965e-6 32.7% Hfo_sOY2+ 2.885e-7 4.8% Hfo_sOH 7.2e-8 1.2%
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