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风化壳离子吸附型稀土矿中稀土元素含量测定与赋存形态研究

Determination of Rare Earth Elements Contents and Study on Occurrence Forms in Weathering Crust Ion Adsorption Rare Earth Ore

  • 摘要: 风化壳离子吸附型稀土矿床具有稀土元素(REEs)种类齐全、放射性活性低、重稀土含量高,且易开采等特点,是一种极为重要的稀土矿床类型。当前,有关该矿床中稀土元素的测定研究大都只测定了稀土元素全量及离子相分量,且有些方法操作流程较繁琐,对于稀土元素的各种赋存形态分析研究较少。但在研究风化壳离子吸附型稀土矿床的成矿规律时,不仅要分析其稀土元素全量,还需要分析影响该矿床中稀土元素的成矿背景、迁移、富集过程中移动差异性、长期性和可利用性的化学形态,因此,准确测定风化壳离子吸附型稀土矿床中稀土元素全量及各赋存形态含量非常必要。本文以五酸混合消解作为测定风化壳离子吸附型稀土矿样品中稀土元素全量的前处理方法,并将BCR法和Tessier法提取的稀土元素形态结果进行对比,以ICP-MS为检测手段,探讨了样品中稀土元素全量及各赋存形态含量分布情况。结果表明,五酸混合消解能将稀土矿样品中所有稀土元素完全溶出,且操作简便,方法精密度(RSD)为0.82%~5.19%,检出限为0.002~0.027μg/g,各元素测定值与认定值的相对误差为−4.70%~6.65%,∑LREEs/∑HREEs为1.25~16.50,涵盖轻稀土和重稀土富集。BCR法和Tessier法提取的稀土元素各形态结果的相对偏差(RD)为0.79%~8.07%,提取结果基本能相互对应吻合,∑REEs回收率为84.75%~107.13%,∑REEs测定值的相对偏差(RD)为0.62%~21.00%,相对误差(RE)小于40%。相较之下,BCR法前处理流程简单,但是划分的形态没有Tessier法直观、具体,无法获取更详细的各形态数据,在本文实验条件下,Tessier法对于稀土元素形态分析可能具有较好的适应性。风化壳全风化层样品中稀土元素主要以离子吸附态赋存在黏土类矿物表面,因而离子交换态含量最高,随着风化壳剖面深度增加,pH升高,稀土元素更容易与碳酸根或碳酸氢根结合,导致碳酸盐结合态中稀土元素含量增大,Ce元素在该层中极易从Ce3+氧化成Ce4+,以沉淀形式滞留于原地,不同于其他稀土元素分异-富集特征,形成Ce异常;而母岩中的稀土元素主要富集在独立矿物晶格中,残渣态含量最高,各赋存形态下所有稀土元素变化规律基本一致。

     

    Abstract: The weathering crust ion adsorption type rare earth deposit has the characteristics of complete REEs types, low radioactivity, high heavy rare earth contents, and easy mining, making it an extremely important type of rare earth deposit. At present, most of the research on the determination of REEs in this deposit only measures the total amount and ionic phase components of REEs, and some methods have complicated operating procedures, while there is relatively little research on the analysis of various REEs forms. However, when studying the mineralization laws of weathering crust ion adsorption type rare earth deposits, it is not only necessary to analyze the total amount of REEs, but also to analyze the chemical forms that affect the mineralization background, migration, enrichment process, long-term differences, and availability of REEs in the deposit. Therefore, it is necessary to accurately determine the total amount and contents of various occurrence REEs forms in weathering crust ion adsorption type rare earth deposits. This article uses five acid mixed digestion as a pretreatment method for determining the total amount of REEs in weathered crust ion adsorption type rare earth ore samples, and compares the results of rare earth elements speciation analysis determined by BCR method and Tessier method. ICP-MS is used as the detection method to explore the distribution of the total amount and various REEs forms in the samples. The results showed that the five acid mixed digestion can completely dissolve all REEs in the rare earth ore sample, and the operation is simple. The precision (RSD) of this method is between 0.82% to 5,19%, the detection limit is between 0.002 to 0.027µg/g, and the relative error between the measured values and the recognized values of each element is between-4.70% to 6.65%. The ∑LREEs/∑HREEs is between 1.25 to 16.50, covering the enrichment of light rare earths and heavy rare earths. After comparing results of the BCR method and Tessier method, The relative deviation (RD) of rare earth various forms extracted by the two methods is 0.79% to 8.07%, and the extraction results can basically correspond and match each other. The rate of recovery ∑REEs is between 84.75% to 107.13%. The relative deviation of ∑REEs determination values is between 0.62% to 21.00%, and the relative error (RE) is less than 40%. In contrast, the BCR method has a simpler pre-processing flow, but the partitioned forms are not as intuitive and specific as the Tessier method, which cannot obtain more detailed data on each form, and under the conditions of this experiment, the Tessier method may have good adaptability for rare earth forms analysis. REEs in the fully weathered layer samples of the weathering crust mainly exist on the surface of clay minerals in the form of ion adsorption, resulting in the highest content of ion exchange state. As the depth of the weathering crust profile increases and the pH rises, REEs are more likely to bind with carbonate or bicarbonate ions, leading to an increase in the rare earth contents in the carbonate bound state. Ce element is easily oxidized from Ce3+to Ce4+in this layer, and remains in place in the form of precipitation, forming Ce anomaly; REEs in the parent rock are mainly enriched in the independent mineral lattice, with the highest residual content. The variation patterns of all REEs under different occurrence forms are basically consistent.

     

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