An Optimized Method for Determination of Ionic-phase Rare Earth Elements by ICP-MS Using Ammonium Sulfate Leaching
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摘要: 离子吸附型稀土中离子相稀土的准确测定对稀土矿体资源评价具有重要意义。离子相稀土以羟基或水合羟基的形式吸附在黏土矿物上，可与强电解质（Mg2+、NH4+等）交换解吸进入溶液。前人以硫酸铵为淋滤液，实现了离子相稀土的解吸、提取，但在溶液浓度、浸取过程等方面选择各异，淋滤浸取率（60%~90%）差异大，未形成高效、统一的浸取方法，不利于离子相稀土元素的精确测定。本文通过对比实验规范了硫酸铵淋滤离子相稀土的各项淋滤参数（固液比、硫酸铵浓度、样品最佳称样量、浸泡时间），减少了淋滤过程中离子相稀土的损失，浸取率达到88%~98%，进而利用ICP-MS测定离子相稀土分量。方法检出限为0.05~5.11 ng/g；三类岩性离子吸附型稀土样品的精密度为：火山岩1.80%~10.01%，变质岩1.06%~7.27%，沉积岩1.72%~7.58%。协作实验室的分析结果验证了本方法的可靠性和准确性。本方法操作简便，分析效率高，为建立相关的行业标准乃至国家标准奠定了基础。
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关键词:
- 离子吸附型稀土 /
- 离子相稀土 /
- 硫酸铵 /
- 淋滤浸取率 /
- 电感耦合等离子体质谱法
Abstract:BACKGROUND The accurate determination of ionic phase rare earths in ion-adsorption rare earths is of great significance for the evaluation of rare earth ore bodies. Ionic phase rare earths are adsorbed on clay minerals in the form of hydroxyl or hydrated hydroxyls and can be exchanged and desorbed with strong electrolytes (Mg2+, NH4+, etc.) into solution. The former used ammonium sulfate as the leachate to achieve the desorption and extraction of rare earth ions in the ion phase, but the solution concentration, leaching process and other aspects of choice, leaching rates (60% to 90%) are different. There is no efficient and uniform leaching method conducive to the accurate determination of ionic phase rare earth elements. OBJECTIVES To establish a high-efficiency leaching process by ammonium sulfate solution and determine the accurate contents of ionic-phase rare earth elements. METHODS The leaching parameters (solid-to-liquid ratio, ammonium sulfate concentration, best sample weight, and soaking time) of rare-earth ions by ammonium sulfate were standardized through comparative experiments, which reduced the loss of ionic phase rare earth during leaching. The leaching rates were from 88% to 98%, and ICP-MS was used to accurately determine the ion phase rare earth component. RESULTS The detection limits are 0.05-5.11 ng/g, and the relative standard deviations (RSDs) are 1.80%-10.01% for volcanic rock, 1.06%-7.27% for metamorphic rock, and 1.72%-7.58% for sedimentary rock. CONCLUSIONS The analytical results of the collaborative laboratory verify the reliability and accuracy of the method. This method is easy to operate and has high analysis efficiency. It provides the base for the establishment of relevant industry standards and national standards. -
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表 1 空白和稀土待测液中稀土元素含量
Table 1. Analytical REE concentration in blank and rare earth solutions
元素 2.5%硫酸铵 3.0%硫酸铵 2.0%硫酸铵 空白待测液
(ng/mL)稀土待测液
(ng/mL)空白待测液
(ng/mL)稀土待测液
(ng/mL)空白待测液
(ng/mL)稀土待测液
(ng/mL)La 0.06 8.79 0.02 8.69 0.02 8.65 Ce 0.10 8.93 0.05 8.71 0.05 8.71 Pr 0.03 9.04 0.01 8.95 0.01 8.95 Nd 0.04 9.29 0.01 9.17 0.01 9.15 Sm 0.04 10.36 0.01 10.34 0.01 10.50 Eu 0.03 10.60 0.01 10.55 0.00 10.56 Gd 0.04 10.10 0.01 10.27 0.01 10.38 Tb 0.02 10.11 0.01 10.41 0.00 10.42 Dy 0.02 10.25 0.01 10.48 0.00 10.60 Ho 0.02 10.12 0.01 10.57 0.00 10.51 Er 0.02 10.40 0.00 10.83 0.00 10.73 Tm 0.02 10.22 0.00 10.79 0.00 10.69 Yb 0.01 10.36 0.00 10.76 0.00 10.71 Lu 0.01 10.20 0.00 10.57 0.00 10.66 Y 0.11 10.85 0.01 11.27 0.01 11.41 
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表 2 方法检出限及测定下限
Table 2. Detection limit and determination limit of elements
元素 方法检出限
(ng/g)方法测定
下限(ng/g)La 2.98 9.93 Ce 5.11 17.02 Pr 0.49 1.64 Nd 2.26 7.52 Sm 0.38 1.28 Eu 0.22 0.75 Gd 0.67 2.22 Tb 0.10 0.32 Dy 0.48 1.60 Ho 0.12 0.39 Er 0.42 1.39 Tm 0.06 0.20 Yb 0.23 0.76 Lu 0.05 0.17 Y 3.50 11.68
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表 3 本研究方法和协作实验室A、B分析离子吸附型稀土样品中的离子相稀土含量
Table 3. Analytical concentrations of ionic-phase rare earth elements in sample HS-1, BZ-2 and CJ-3 determined by this study and collaboration laboratory A, B
元素 样品HS-1 样品BZ-2 样品CJ-3 本方法
测定值
(μg/g)RSD
(%)实验室A
测定值
(μg/g)实验室B
测定值
(μg/g)本方法
测定值
(μg/g)RSD
(%)实验室A
测定值
(μg/g)实验室B
测定值
(μg/g)本方法
测定值
(μg/g)RSD
(%)实验室A
测定值
(μg/g)实验室B
测定值
(μg/g)La 464.76 1.80 463.73 456.67 156.39 3.70 162.67 159.33 342.87 1.72 349.87 339.33 Ce 4.61 5.63 4.31 4.84 5.91 4.72 5.82 6.30 12.44 2.10 12.16 12.40 Pr 95.16 5.01 92.52 90.47 28.90 2.65 29.65 28.47 73.82 6.17 70.75 68.43 Nd 345.60 4.41 334.93 331.67 101.21 3.46 101.87 98.43 252.38 2.77 250.13 246.67 Sm 69.97 6.94 68.08 66.17 17.84 3.77 17.49 17.13 56.41 7.58 54.21 52.43 Eu 6.29 4.59 6.22 6.13 3.30 2.22 3.39 3.27 4.29 3.12 7.01 6.83 Gd 59.74 8.74 66.59 53.57 19.10 4.45 18.16 14.67 58.22 7.10 59.33 47.30 Tb 9.17 7.06 8.96 8.36 2.52 3.20 2.60 2.49 9.41 6.48 9.57 8.97 Dy 46.47 6.07 45.07 43.83 14.33 1.06 14.43 14.37 58.05 4.59 56.00 55.67 Ho 7.98 5.52 7.72 7.53 2.66 2.10 2.69 2.73 11.02 4.93 10.59 10.57 Er 19.93 9.16 19.73 19.63 7.14 3.70 7.30 6.75 30.16 6.98 30.08 27.87 Tm 2.32 10.01 2.17 2.14 0.83 6.78 0.86 0.88 4.15 3.82 3.98 4.23 Yb 12.05 6.47 11.95 11.20 4.64 6.25 4.82 4.83 25.84 4.84 24.77 26.17 Lu 1.55 7.63 1.55 1.39 0.54 7.27 0.57 0.55 3.50 3.97 3.39 3.40 Y 221.34 7.83 226.40 199.67 74.98 5.81 81.33 71.57 323.42 6.03 352.53 307.33
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